tal Monitoring Systems Ne27711 77-027 July 1984 Quality Assurance Handbook for Air Pollution Measurement Systems: Volume II. Ambient Air Specific Methods Sections 2.1, 2.2, 2.6, and 2.9April 1984 i Section 20 2.0.1 2.0.2 203 2.0.8 205 206 207 208 209 2.0.10 2.011 2.0.12 24 3 Volume II Table of Contents Purpose and Overview of the Quality, Assurance Handbook General Aspects of Quality Assurance for Ambient Air Monitoring Systems Sampling Network Design and Site Selection Sampling Considerations Data Handling and Reporting Reference and Equivalent Methods Recommended Quality Assurance Program for Ambient Air Measurements Chain-of-Custody Procedures for Ambient Air Samples Traceability Protocol for Establishing ‘True Concentrations of Gases Used for Calibration and Audits of Air Pollution Analyzers {Protocol No, 2) Calculations to Assess Monitoring Data for Precision and Accuracy for SLAMS and PSD Automated Analyzers and Manual Methods Specific Guidance for a Quality Control Program for SLAMS and PSD ‘Automated Analyzers and Manual Methods USEPA National Performance Audit Program ‘System Audit Criteria and Procedures for Ambient Air Monitoring Programs ‘Audit Procedures for Use by State ‘and Local Air Monitoring Agencies Reference Method for the Determination of Sulfur Dioxide in the Atmosphere (Pararosaniline Method) Procurement of Equipment and Supphes Calibration of Equipment Preparation of Reagents ‘Sampling Procedure Analysis of Samples Data Reduction, Validation and Reporting Maintenance Auditing Procedure ‘Assessment of Monitoring Data for Precision and Accuracy Recommended Standards for Establishing Traceability Reference Method Roferences Data Forms Pages 5 23 13 " 18 27 86 101 Ban soado Date 12-30-81 7.01-79 7-01-79 7-01-79 7-01-78 7-01-79 7-01-79 6-15-78 313-79 7-01-79 7-79 7-01-79 7-01-80 7-01-80a April 1984 Table of Contents (continued) Section Pages Date 2.2 Reference Method for the Determination of Suspended Particulates in the Atmosphere (High-Volume Method) 2.2.1 Procurement of Equipment and ‘Supplies 2 1-10-83, 2.2.2 Calibration of Equipment 13 1-10-83 2.23 Filter Selection and Preparation 4 1-10-83 2.24 Sampling Procedure a 1-10-83, 2.2.5 Analysis of Samples 1 1-10-83 2.2.6 Calculations and Data Reporting 2 1-10-83 2.2.7 Maintenance 2 1-10-83 22.8 Auditing Procedur 4 110-83 2.2.8 Assessment of Monitoring Data for Precision and Accuracy 1 1-10.83 2.2.10 Recommended Standards for Establishing Traceability 1 1-10-83 2.2.11 Reference Method 10 1-10-83 22.12 References 1 1-10-83 2.213 Data Forms 10 1-10-83, 2.3 Reference Method for the Determination of Nitrogen Dioxide in the Atmosphere (Chemiluminescence) 2.3.1 Procurement of Apparatus and Supplies 8 7-01-79 2.3.2 Calibration of Equipment 27 7-01-79, 2.33 Operation and Procedure 10 7-01-79 2.34 Data Reduction, Validation and Reporting 5 7-01-79 2.3.6 Maintenance 2 7-01-78 2.36 Auditing Procedure 12 7-01-79 2.3.7 Assessment of Monitoring Data for Precision and Accuracy 1 7-01-78 2.3.8 Recommended Standards for Establishing Traceability 1 7-01-79 2.3.9 Reference Met 9 7-01-79 213.10 References, 1 7-01-79 23.11 Data Forms 7 7-01-79 2.4 Eqivalent Method for the Determination of Nitrogen Dioxide in the Atmosphere (Sodium Arsenite) 2.4.1 Procurement of Equipment and Supplies 6 12-30-81 2.4.2 Calibration of Equipment 13 12-30-81 2.4.3 Preparation of Reagents 3 12-30-81 2.44 — Sampling Procedure 10 12-30-81 245 Analysis of Samples 13 12-30-81 2.4.6 Data Reduction, Validation and Reporting 3 12-30-81 2.4.7 Maintenance 2 12-30-81 2.48 Auditing Procedure " 12-30-81 2.49 Assessment of Monitoring Data for Precision and Accuracy ‘ 12-30-81April 1984 i Sect 2.4.10 24.11 2412 2.413 25 26.10 24a 274 272 273 274 278 Table of Contents (continued) Recommended Standards for Establishing Traceability Equivalent Methods References Data Forms. Equivalent Method for the Determination of Sulfur Dioxide in the Atmosphere (Flame Photometric Detector) Procurement of Apparatus and Supplies Calibration of Equipment Operation and Procedure Data Reduction, Validation and Reporting Maintenance Auditing Procedure Assessment of Monitoring Data for Precision and Accuracy Recommended Standards for Establishing Traceability Equivalent Method References Data Forms. Reference Method for the Determination of Carbon Monoxide in the Atmosphere (Non- Dispersive Infrared) Spectrometry Procurement of Equipment and Supplies Calibration of Equipment Operation and Procedure Data Reduction, Validation and Reporting Maintenance Auditing Procedure Assessment of Monitoring Data for Precision and Accuracy Recommended Standards for Establishing Traceability Reference Method References Data Forms Reference Method for the Determination of Ozone in the ‘Atmosphere (Chemiluminescence) Procurement of Equipment and Supplies Calibration of Equipment Operation and Procedure Data Reduction, Validation and Reporting Maintenance Pages 10 2 40 Date 12-30-81 12-30-81 12-30-81 1230-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81April 1984 Section 2.78 277 278 279 Table of Contents (continued) Auditing Procedure “Assessment of Monitoring Data for Precision and Accuracy Recommended Standards for Establishing Traceability Calibration of Ozone Reference Methods References Data Forms. Reference Methad for the Determination of Lead in Suspended Particulate Matter Collected from ‘Ambient Air (Atomic Absorption Spectrometry) Procurement of Equipment and Supplies Calibration of Equipment Filter Selection and Procedure ‘Sampling Procedure Analysis of Samples Calculations and Data Reporting Maintenance Auditing Procedure ‘Assessment of Monitoring Data for Precision and Accuracy Recommended Standards for Establishing Traceability Reference Method References Data Forms. Reference Method for the Determination of Sulfur Dioxide in the Atmosphere (Fluorescence) Procurement of Apparatus and Supplies Calibration of Equipment Operation and Procedure Data Reduction, Validation and Reporting Maintenance Auditing Proceduré ‘Assessment of Monitoring Data for Precision and Accuracy Recommended Standards for Establishing Traceability Equivalent Method References Data Forms. Pages 8 1 1 13 13 Noo Date 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81 12-30-81Jan. 1983 United States Environmental Protection Agency ction 2.1.0 Environmental Monitoring Systems Laboratory Research Triangle Park NC 27711 Research and Development EPA-600/4-77-027 Test Method Section 2.1 Reference Method for the Determination of Sulfur Dioxide in the Atmosphere (Pararosaniline Method) Outline Section Summary Method Highlights Method Description 1. Procurement of Equipment and Supplies Calibration of Equipment Preparation of Reagents ‘Sampling Procedure Analysis of Samples Data Reduction, Validation, {and Reporting 7. Maintenance B. Auditing Procedure 9, Assessment of Monitoring Data for Precision and Accuracy 10. Recommended Standards for Establishing Traceability 11. Reference Method 12. References 13. Data Forms Summary When sulfur dioxide (SO) is ‘absorbed from ambient air into a solution of potassium tetrachloromercurate (TCM), 2 monochlorosulfonatomercurate ‘complex (MSM) is formed that resists, oxidation by oxygen in the air. This, complex can be considered stable at 18°410°C only during sampling. The Number of Documentation Pages 24 1 21 1 244 3 242 14 213 4 214 10 215 7 216 4 247 1 218 4 219 2 2.1.10 1 241 " 2442 1 2113 16 sample then must be stored at 5°C until analysis to prevent any further degradation. (Thermally controlled sampling equipment is commercially available.) The MSM is reacted with pararosaniline (PRA) and formalde- hyde to form an intensely colored dye (pararosaniline methyl sulfonic cia) and the absorbance of the dye is ‘measured spectrophotometricaly.Jan, 1983 This method can be used to determine SO- levels in ambient air during sampling periods ranging from 30 min to 24 h. The detection limit for the method 1s 25 yg SO:/m! (0.01 pm) in an air sample of 30 standard liters (short-term sampling) and 134g S0z/m? (0 008 ppm) in an air sample of 288 standard liters (long-term sampling) ‘Based on extensive review and on experience gained in aueits and in Collaborative tests,’* the PRA method description and the recommended limits for quality checks and audits presented herein sometimes differ from and supersede those in the ‘guideline document.’ On the other hand, that document contains functional and error analyses that are not included in this Handbook ‘A copy of the Reference Method 1s in Section 2.1.11 Blank data forms in Section 2.1.13 are for the Convenience of the Handbook user Recommended equivalent methods are published in the Federal Register and quarterly in the Quality Assurance Newsletter issued by the US. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268. See Section 2.04 of this, volume of the Handbook for a discussion of equivalency concepts, Method Highlights In this quality assurance document for the SO, Reference Method, the procedures are designed to serve as Quidelines for the development of agency quality assurance programs Because recordkeeping is a critical part of quality assurance activities, several data forms are included to aid in the documentation of necessary data. The blank data forms (Section 2.3.13) may be used as they are, or they may serve as guidelines for preparing forms more appropriate to the individual agency; partially filed: in forms are interspersed throughout the text of the method description to illustrate their uses. Activity matrices ‘at the end of pertinent sections can be used for quick review of the material covered in the text sections Following 1s a brief summary of the material covered in this SOz method description 1. Procurement of Equipment Section 2.1.1 deseribes the selection ff equipment and the performance of procurement and calibration checks of the equipment; all are prerequisites for a quality assurance program. ‘Section 2.1.1 conveniently identifies the sections/subsections of this part of the Handbook that pertain to specific equipment and supplies, and Figure 1.1 provides an example of 2 permanent procurement record. 2. Calibration of Equipment Section 2'1 2 provides detailed calibration procedures for flow measurement equipment, analytical balance, timer, and elapsed-time meter This section can be removed, along with the Corresponding sections of the other methods of this volume, to serve as a calibration handbook, Table 2.4 at the end of Section 2.1.2 provides 2 summary of the acceptance limits for calibration This section is unique ia that it contains detailed calibration procedures for almost all flow Measurement equipment used in ambrent air sampling and analysis. 3._ Preparation of Reagents Section 2.1 3 describes the preparation and handling of reagents Reagents must bbe carefully prepared, stored, and ‘maintained fresh (.e., within the acceptable limits of shelf life). Table 3 1 at the end of this section summarizes the important activities for their preparation and storage. 4. Sampling Procedure Section 2.1.4 provides a detailed description of the Selection and assembly of the ‘apparatus and the checkout of the performance. The operator must perform the initial and final flow measurements and should perform the operational checks fisted in Subsection 4.3 1 before collection of the sample and the postsampling checks listed in Subsection 4.3.2 after the sample collection The daia record form (Figure 4.10 of Section 2.1.4) ‘summarizes the information required to ensure the availabilty of good quality data and background information Because the SO-TCM complex 1s thermally unstable, the Oz concentration depends greatly on the temperature history of the TCM absorbing solution. The user of this method should also refer to Reference B in Section 21.12. 5. Analysis of Samples Section 2.1.5 contains a step-by-step procedure for colorimetric analysis, acceptance limits for the calibration curve, traceability check, and laboratory data log. The appropriate limits are given in Table 6.2 at the end of Section 2.1.5. 8. Data Reduction, Validetion, and Reporting Section 2.1.6 describes those activities pertaining to data calculations and reporting, An important part of a quality assurance program is the final data review, the data edit or validation, and the use of standardized reporting procedures. Independent checks of the data and caleulations are recommended to ensure that the reported data are both reurate and precise, 7. Maintenance Section 2.1.7 recommends periodic maintenance schedules to ensure that the equipment is capable of performing in accordance with specifications. 8. Assessment of Data for Accuracy and Precision Section 2.1.8 and 2.1.9 describe the assessment of the data for accuracy and precision, respectively, Independent audit activities. provide accuracy checks of the flow rate measurements, the analysis process with the use of reference samples (EPA audit ‘samples), and the data processing The precision check is performed by Using @ collocated sampler as a reference. The expected agreement between two collocated sampling trains is given in Table 9.1 and Figure 91 of Section 2.1.9. 9. Reference Information Section 2.1.10 discusses the traceability of measurements to established standards of higher accuracy, a necessary prerequisite for obtaining accurate data Sections 2.1.11 and 2.1.12 contain the Reference Method and pertinent references, ‘Section 2.1.13 contains blank data forms for the convenience of the user.Jan. 1983 1 Section 2.1.1 1.0 Procurement of Equipment and Supplies Specifications for the sampling equipment and for the analytical and the support supplies for monitoring sulfur dioxide (S02) in ambient air are described in Section 2.1.11. The list below references the sections/subsections of this Handbook to help the user find specific information needed for procuring the equipment and supplies. tom Section Subsection Calibration information Wet test meter 212 244 ‘Soap bubble meter 212 212 ‘Mass flow meter 212 213 Rotameter 212 214 Flow-contro! devices 212 22 Analytical balance 212 23 Elepsed-time meter 212 24 Timer 212 25 Preparation of Reagents 213 34-314 Sampling Procedure Absorber 214 A2ZIG2I, 425-427 ‘A 24-h bubbler train 214 426 Temperature-controlled 2n4 426 ‘shelter Critical orifice 214 42.7 Vacuum pump 214 43.1432 Moisture trap 214 43.2 Timer 204 431,432 ‘Membrane particulate filter 214 43.2 Analysis of Samples ‘Spectrophotometer 215 52.53 Maintenance A 24-h bubbler train 207 a ‘Short-term sampling train, 217 22 ‘The quality assurance functions are summarized in Table 1.1. Upon receipt of the sampling equipment, apparatus, ‘and supplies, the procurement checks described in Table 1.1 should be performed. Al pertinent procurement, disposition, and check information. should be recorded in a log such as the one shown in Figure 1.1. This log will serve as a permanent record for future procurement needs, provide continuity among users of equipment ‘and supplies, and provide a basis for fiscal projections.Jan, 1983 Section 2.1.1 saLysnpuy 0% Lo) JaPol/ oq) ufoife | usfizfe | somoys| bicio| fp | dwnd wanowp 10D peneoey ‘Palepi TopuaR paee | rican ‘wondiasep wei aE aoJan. 1983 3 Section 2.1.1 Tablet. Activity Matrix for Procurement of Equipment and Supplies Action it Frequency and method requirements Equipment Acceptance limits ‘of measurement are not met Absorber Reference Method, Upon receipt, check Return to supplier. Sec 2.1.11 performance. Vacuum pump Capable of maintaining an Upon receipt, check Return to supplier. air pressure differential performance. 50.7 atmosphere ot desired flow rate Air flow contro! device Capable of controlling air Check upon receipt: Adjust using manufac: How within 8% over the Sec. 2.2. turer's instructions, or length of the sampling return to supplier. period Spectrophotometer Suitable for measuring Verity wavelength calibra- Request calibration check ‘absorbance at 648 +5 nm tion upon receipt and after by manufacturer/ supplier. with an effective spectral every 160 hof use or every band width <15 nm 6 months, whichever comes first, using NBS traceable ‘standard wavelength fitter. Flow measurement devices ‘For acceptance limits rela- Upon receipt, conduct See Table 2.4 (wet-test meter. soap-bubble tive to calibration checks, calibration check. ‘meter, mass-flow meter, rota- see Table 2.4 ‘meter, flow-comtro! devices, analytical balance, elapsed: time meter, timers)Jan, 1983, 1 Section 2.1.2 2.0 Calibration of Equipment Before beginning the SOs sampling and analysis, be sure to calibrate the ‘sampling and analysis equipment. The calibration activities are summarized in Table 2.4 at the end of this section. Many of these calibration checks should also be used for the initial procurement activities All data and calculations in the calibration activities should be recorded in a separate calibration log: that is, the log should be arranged so that a separate section is designated for each calibrated apparatus and sampler 2.1. Calibration of Flow Measurement Equipment The sampling procedure for determination of SOs in ambient air can be implemented by use of one of two basic sampling trains. The differences between the two sampling trains are the flow rate, absorber design, and flow control system. The short-term sampling train consists of all glass midget impingers and utilizes either a needle valve or critical orifice to control the flow. Short-term sampling periods range between 30 minutes and 3 hours and utilize flow Fates of 900 to 1100 em*/min for 30: ‘minute samples to 450 to 550 em#/min for 1- to 3-hour samples. The long-term sampling train consists of a polypropylene absorber tube with @ glass impinger stem and utilizes a eritical orifice to control the flow. The sampling period is 24 hours, and the flow is between 180 to 220 em?/min ‘Although both trains have a flow: controlling device that must be Calibrated to obtain the appropriate range for the sampling rate, these devices cannot be used to measure the actual sampling flow rate, The actual sampling flow rate 1s determined on site betore and after each sampling period by use of an appropriate flow-measuring device that is not part of the sampling train. Typical flow measuring devices are wet-test meters, soap-bubble meters, mass-flow meters, and rotameters— all of which require calibration 2.1.1 Wet-Test Meters — Calibration Check - Wet-test meters are calibrated by the manufacturer to {an accuracy of 40.8 percent: the calibration must be checked initially (upon receipt) and quarterly thereafter at standard temperature and pressure and at the flow rates at which the meter will be used. The following liquid positive-displacement technique ‘can be used to verify and make any adjustments to the accuracy of the wettest moter to +1 percent. 1. Level the wet-test meter by adjusting the legs until the bubble on the top of the meter is centered 2. Adjust the water volume in the ‘meter until the pointer in the water level gauge just touches the meniscus. Refer to manufacturer's Instructions because some types of meters may require additional adjustments. 3. Adjust the water manometer in the ‘meter to zero by moving the scale or by adding water to the manometer. 4. Set up the calibration apparatus as shown in Figure 2.1. Do not attach the saturator at this time. 2. Fill the 8-gal jug (the reservoir) with distilled water almost up to the air inlet tube, and allow it to equilibrate to room temperature (about 24 hh) before use. Thermometer Air inlet Figure 2.1 . Start water siphoning through the system at a flow rate of approximately 200 ml/min, collect the water in a T-gal container located in place of the volumetric flask (Figure 2.1). 5. Check the physical operation of the meter. If the manometer reading is <10 mm (<0.4 in.) H2O, the meter i in proper working condition. Continue to Step 6. If it is >10 mm (04 in.) HO, the wet-test meter is defective. Return it to the manufacturer for repair if the defect(s) {e.g., bad connections or joints) cannot be found and corrected, 6. Attach the saturator and continue the operation until the 1-gal container is almost full, and then use a pinch clamp to turn the siphoning system nd 7. Read the initial volume (V) from the wet-test meter dial, and record it (on the wet-test calibration log (Figure 2.2) 8. Place a clean, dry, 2000-mt volumetric flask (Class A) under the siphon tube; open the pinch clamp; and fill the flask to the 2000-ml mark Thermometer Woter Reservoir (8-92! joa) Velve Water In }2000-mi Line Volumetric Flask (Class A) Catbration check apparatus for wet-test meter.Jon. 1983 ‘Boy vonesqyes seiow 121 wm ez oun g 01 pappe 29 01 51 “ay 4 ‘worsks uoperyes yBnosy paysnd DON FABRA 7S] tA “% pe00x8 0} JOU J01N8 Ua0v0d ebe:eAy by wi OPE = BELO * OF x unl -S =a WB 2600 + 90 FRE "A 2602001 x =8f A= soe werieg ee Sa A rae Brinn Section 2.1.2 az A re F irae Oy ua e ¥ Je Ty und | TRL Ta) 1801 ‘trag) 6upeas 1 warowoueW aunowoveg 7a cor 1 euinjon ysey 1804 rer Bo 9 am 0 aaa caer eo) iy i 19 Pat0s9, air s0umzeyrveyy saizts 1800 0mJan. 1983 3 Section 2.1.2 8. Record the manometer reading While the water is flowing. Also record the following dat Meter and reservoir air temperatures, °C (°F), and . Barometric pressure, mm (in.) Hg 10. When the volumetric flask reaches its calibrated capacity, read 1¢ final volume (Vi) from the wet-test meter dial and record. Calculate the indicated volume measured by the wet-tost meter (Vi = Vi - Vj) 11, Repeat steps 7 through 19 twice, 12. Calculate the volume passing through the meter (Vi), using Equation 2-1, for each test. eee Equation 2-1 where P. = barometric pressure, mm Hg ‘AP»=wet-test meter manometer read- ing. mm Hg jemperature of reservoir, K= 273.2 T= temperature at wet-test meter K=°C+273.2 Vi = volume measured by volumetric ‘ask, liters. ‘An example of this calculat ec Barometric pressure, Pa = 742.2 mm Hg Reservoir temperature, T, = 23.0°C + 273.2 = 296.2 K Meter temperature, Tm = 225°C + 273.2 = 298.7K Meter manometer reading = 35 mm H.0 APm= 35 mm HzO x 0.074 mm Hg/mm Hz0 = 2.6 mm Hg: ‘Volume measured by wet test meter Vat"#= 2.020 - 0.005 = 2.016 liters. Volume measured by volumetric flask, Vi = 2.0000 liters Corrected volume at meter condi- tions: Vn (Fen) 2.000 = 1.9966 liters. 296.2 13, Calculate the relative percent error 08 follows: error: ((et:¥et) 100 vor (as Pa 2288) 100=0.92%, 1.9966 Equation 2-2 or should not exceed +1 percent. If it does, check all connections within the test apparatus for leaks; gravimetrically check the volume of the standard flask: and repeat the calibration procedure. If the the specifications in the manufacturer's manual are met or return the meter to the manufacturer. Use of the wet-test meter for the calibration of flow rate devices such 2a rotameters and mass-flow meters requires corrections for temperature, barometric pressure, and possibly the pressure of the water. If the device to be calibrated is placed after the wet-test meters (as shown later in Figure 2.5), no correction for the vapor pressure of water is required. Equation 2-3 is presented to assist the user with these corrections to the standard conditions of 760 mm (29.92 in.) Hg, 25°C (77°F), and O percent water vapor Flow rate at standard conditions vol (mi)_xP= Py 298 time (min) 760° 273 +T Equation 2-3 where stmospheric pressure, mm Hg, fapor pressure of water (see Table 2.1 on next page) mm Hg, and = temperature of gas, °C Example: Assume the temperature to be 20°C and the atmospheric pressure to be 710 mm Hg, Flow rate at standard conditions =_vol {ml)_,710- 17.54, _298 time (min) 760273 +20 = vol (rnll_ 0.927 = ml/min, time (min) 2.1.2 Soap-Bubble Meter - Calibration checks - Soap-bubble meters calibrated by the manufacturer to an accuracy of +0.25 percent are -ommercially available; the volume of ach of these soap-bubble meter tubes is traceable to a National Bureau of Standards (NBS) displacement volume. Frequently, however, soap- bubble meters are constructed in the laboratory by use of a burette of ‘appropriate volum Two calitration methods a ‘commonly used for soap-bubbl ‘meters: (1) the volume-displacement method described for the wet-test ind (2) the volume- ment method measured metrically. The gravimetric displacement method requires less effort than the volume-displacement method. The displacement volume of 2 soap bubble meter does not change with use; therefore, it requires only initial calibration upon receipt from the manufacturer. The soap-bubble meter can be used only within the volume range for which it was calibrated. A calibration procedure by the gravimetric method is presented here. 1. Secure a clean displacement tube to a ringstand, and attach 3 stopoock to the bottom (as shown n Figure 2.3), Soap-Bubble Meter Tube ae Displacement Volume ‘Stopeoek Ground-Glass Stoppered Flask Figure 2.3 Test apparatus for soap: bubble meter 2. Obtain an appropriately sized and stoppered groundglass volumetric flask that will contain the volume of the displacement tube of the soap: bubble meter. 3. Determine the weight of the flask and the stopper to the following specifications: '2, 10-ml flask - weigh to the nearest 0.001 g . 100-ml flask - weigh nearest 0.01 g ©. 1000-ml flask nearest 0.1 9 Record the weight on the calibration log, Figure 2.4; a blank form for the Handbook user is in Section 2.1.13, 4. Fill the displacement tube with distilled water, drain the system until all air bubbles are removed, and collect the water in @ beaker and discard it, 5. Fill the displacement tube so that, the bottom of the meniscus is at the top mark, 6. Determine the temperature of the water within the displacement tube, and record it in the log, to the weigh to theSection 2.1.2 Jan. 1983 Table 2.1 lytsnot =NOAG OVOO ° COND awnsol 0.0 1.436 1.560 1.691 1834 1.987 2149 2.326 2514 2716 2931 3.163 3.410 3.673 3.956 4.258 4.579 4579 4926 5.294 5.685 6.107 6.543 7.013, 7513 8.045 8.609 9.209 9.844 10.518 11.231 11.987 12.788 13.634 14530 15.477 16.477 17.536 18.650 19.827 21.068 22.377 23.756 26.209 26.739 28.349 30.043 91.824 33.695 35.663 97.729 39.898 42.175 44.563 497.067 49.692 Saturation Vapor Pressure Over Water (°C, mm Hg) (Values for fractional degrees between 50 and 89 obtained by interpolation) a2 os op op "oo 02 04 06 op 2.887 28463 eee aoe ‘St 97.20 98.2 99.1 100.1 101.7 guys goo 20 ee 310593 foes fags toe Nha 4196 4135 4075 4.016 = 56 123.80 «1250 «126.2 :«—«1274 «1286 4513 sue 4308 aio HBO Hak aes 4647 4715 «4.785 4.855 5914260 143.9 «145.2 «146.6 «148.0 get ome an arJan. 1983, 5 Section 2.1.2 Table 2.1 (continued) Saturation Vapor Pressure Over Water (°C, mm Hg) Walues for fractional degrees between 50 and 89 obtained by interpolation) Temp °c___0.0 02 os (ogee oat 0.0 02 04 06 08 3962442 63.009 53.580 64.156 64737 733.24 738.53 743.85 749.20 764.58 40 85.324 5591 56.51 57.11 57.72 100 760.00 765.45 77093 77644 782.00 4158.34 58.96 6958 6022 60.86 ‘101 __‘78757 793.18 798.82 804.60 810.21 L Secret 4 2sblet ee Final sone weget of wate ont Displacement i, he ws fia value omarts / 23 73,905__| (73-730 100,27 2 23 73.405 173.935 100.27 3 [23 73.905, (73.925 100.26 al Y= dpacomen sol sta oy maputerr ve WW FO ST SBMS. 221 Oo re 97S Toe Vat Vea* Ve 7+ (00,27+(002% ao, 267 3 3 swerror=(¥= 100 0,246, not to exceed 21%. Ve Figure 2.4 — Soap-bubble meter calibration log. 7. Drain the displacement volume WW The following example calculation is into the weighed flask (Step 3), and Equation 2-4 for a 100-ml displacement tube. immediately cap it with a ground- where 2. Water temperature = 23.0°C glass stopper. Ve" displacement volume, ml b. Wt, =73.905 g 8. Weigh the flask and its contents, Wtv= final weight of water and. ¢. Wti= 173.930 g and record the weight in the log. flask. 9 4d. D, = 0.99756 (Table 2.2) 9. Repeat Steps 3 through 8 twice. Wt.= initial weight of flask, 9 10. Calculate the displacement D,=relative density of water at 173.930 - 73.905 = 100.27 mi volume (Va), using Equation 2-4. test temperature, g/ml 0.99766Section 2.1.2 6 Jon. 1983, 11. Compute the average displace- ‘ment volume (Va) from the three tests: Vas + Vee + Ves 3 Va Equation 2-5 12. Compute the percent error as follows 100 Equation 2-6 where V is the displacement volume (mi) stated by the manufacturer. The example calculation of % error below assumes that V= 100 mi and Ve 100.287 seerrori00-100, 261) 100.267 x 100 = -0.27%, The error should not exceed +1 percent, Use of the soap-bubble meter for the calibration of flow rate devices Such as rotameters and mass-flow meters requires corrections for temperature, barometric pressure, land the vapor pressure of the soap bubble (which 1s considered to be the ‘vapor pressure of water). Equation 2-3 is repeated here to assist the user with these corrections to the standard conditions of 760 mm (29.92 in.) Ha, 25°C (77°F), and 0% water vapor. Flow rate at standard conditions —vol(mi}_yP-Pax_298 time (min) 760 273+ Equation 2-3 (repeated) where imospheric pressure, mm Hg apor pressure of water (see Table 2.1), mm Hg temperature of gas, °C Example: Assume the temperature to bbe 20°C and the atmospheric pressure 10 be 710 mm Hg Flow rate at standard conditions vol (mi) 47 4 x _298 Time (mis) 760-273 +20 VoL) .0,827 = mI/min Time (mi 2.1.3 Mass-Flow Meter Calibration Check - Mass-tlow meters operate ‘on a thermal principle that depends ‘on the mass flow of the gas and on its heat capacity to gauge the temperature within @ heated conduit Because these meters measure the true mass flow, they have the advantage of not requiring corrections for changes of temperature and pressure. Flow rate values are usually given in standard cubic centimeters of air per minute, which are measures of the volume occupied by 2 mass of 2 at standard temperature and pressure, 8 specified by the manufacturer Mass-flow meters are not volume displacement devices; therefore, they require calibration at least quarterly ‘against a displacement device such as, a bubble meter or a wet-test meter, Which serves as a secondary calibration standard. Before calibration of a mass flow meter against an already calibrated wet test meter, reference should be made to the manufacturer's insteuctions for the flow rate capacity. The following procedure should then be used. 1. Be sure that the mass flow meter is off, Use the adjustment screw below the meter face to set the pointer needle on zero, 2. Turn the meter on, and allow it to warm up for 1h 3. After the warmup period, adjust te electronic zero as follows 2. Plug the inlet and the outlet of the transducer b. Use the adjust screw to set the electronic zero on the meter ©. Unplug the ends of the transducer before connecting it to the test apparatus (as illustrated in Figure 25), ‘4. Turn the vacuum pump on, and use the needle valve to adjust the Thermometer Air (oles |S Figure 2.5 flow rate to approximately 75 percent of the full scale of the mass-flow meter. 5. Allow the system to equilibrate for approximately 10 revolutions of the wet-test meter. 6. Read the manometer on the wet- test meter in mm HzO: convert to mm Hg {mm HzO x 0.0738 = mm Hg); and record the Apm on the calibration log (Figure 2.6). Because the air passing through the calibration apparatus has been presaturated, no correction for water vapor is necessary 7. AS the wet-test meter pointer passes zero, use a precision ‘stopwatch to begin the timing. As the wet-test meter pointer passes the three-quarter revolution mark, take @ reading and record the mass-flow meter reading in the log. As the wet- test meter pointer passes the starting point, stop the stopwatch and record the elapsed time (0) 8, Record the wet-test meter volume in the column headed by Vy, and record the wet-test mater fluid temperature (Ta) in K. 9, Calculate Pm = Pp - APm and use Equation 2-7 to calculate V, by using the recorded value of Py Tr and Vas T, = 298 K and P, = 760 mm Hg Record the Vs value Va= (Pats Wm Equation 2-7 PT, Mase-Flow Meter Face ‘Mass-Hlow meter calibration apparatus.Section 2.1.2 Jan. 1983 oy uonerqyes wow mey-sseny 9 zembig _ a _|- | eo _ ——— a | = ae a a ae ee : 7 _ eee —_ __ “ = [OE ~ | - SS ee 9 + ea —L € a 7 z SO | Baro or boELO O7- [x9 bp. EL 0 1 ae ara ona) are Tal TP tana Guu ae) | ioe a pats “anpgetA |paaeydsip ausnyap| wav dae eel mL sew Rt oe _ a 0 ers 92000 = 04 ss a rgcg ata HELIS yop Ma paverare9 pice © thing omicrry pg ha) aiseond aaworeg cg Rrorncusoy woos orgy ‘uoae907 SLA AES [=I T vn PRS 9 apr “a (we ices mony SSHSection 2.1.2 8 Jan. 1983 Rotameters can be calibrated by use where AP = measured of a bubble meter as a secondary Vin= measured volume from bubble barometric pressure corrected standard as follows meter, mi for internal meter pressure, mm conditions, 760 mm Hg ‘measured temperature of arr, K lemperature at standard conditions, 26°C = 298 K and Vn= measured volume from wet test meter, 10. Calculate the flow rate (. from V, and Equation 2-8 where (Q,= flow rate at standard conditions, liters/min V.= volume of gas at standard conditions, titers Record Q.. 11 Plot Q, versus the mass-flow meter readings on rectangular graph paper. 12. Repeat Steps 6 through 11 for five other flow rates within the range of the mass-flow meter. 13. Construct a best-fit curve for the points generated, and use this relationship for future work using the mass-flow meter. 2.1.4 Calibration of Rotameter - & ‘commonly used method for measuring gas flow rates 1s the rotameter or variable-area flow meter. Its usually 2 round glass tube housing one or more floats that are free to move vertically up and down the tube axis, (On the sides are reference marks, which may be either linearly or exponentially inscribed on the tube As the gas flows up the tube, the float 's displaced and continues to move Upward until equilibrium is reached This.occurs when the gravitational force of the float equals the buoyant force of the moving gas stream. Float design will vary depending on the manufacturer and the flow rate desired, Most lower-range rotameters use spherical floats. Readings are conventionally taken at the widest point of the float Although the manufacturer generally provides reasonably accurate calibration curves, rotameters should be recalibrated at the conditions that will be used Rotameters separate from the train used as flow measuring devices must be calibrated against a previously calibrated wet-test meter, soap bubble ‘meter, or mass-flow meter. 1 Assemble the equipment as shown in Figure 2.7, Note Fotameters calibrated in a vacuum situation should be used only na similar (vacuum) situation 2. Read and record room temperature and barometric pressure fon the rotameter calibration data form (Figure 2 8 on following page) 3 Turn on vacuum pump 4. Adjust the needle valve until the rotameter float i$ about 20 percent of full scale 5 Touch the surface of the soap solution wath the open end of the bubble moter so that a soap bubble ‘all start to travel up the bubble meter tube. Repeat several times or until bubbles will travel the full length of the tube without breaking 6 Touch the surface of the soap solution with the open end of the bubble meter so that a single bubble starts to travel up the bubble tube When the bubble passes the first hne of graduated scale, start stopwatch Record time and volume displaced. 7. Repeat Step 6 two more times Record time and volume each time. 8. Calculate average time and volume displacement for three runs, 9. Correct average volume displacement to standard conditions of 760 mm Hg and 25°C by use of Equation 2-9, [Beaker with \\ | sea Nf serene Figure 2.7 ‘Volume tubes avaible 10 ml to 1000 mi Equation 2-9 P.= barometric pressure, mm Hg P= vapor pressure of water in ‘soap bubble meter at the temperature employed, mm Hg (see Table 2.2) P.= pressure at standard conditions 760 mm Hg temperature at standard conditions, 298 K Too= temperature of soap bubble meter, K. 10, Divide the corrected volume displacement by the average time to determine the flow rate. 11. Repeat Steps 4 through 10 for each of five of more uniformly spaced points on the rotameter scale, going from low values to high values. 12, Plot the rotameter units versus the flow rate Q, on linear graph paper, constructing a best fit smooth curve through the data points by use of a flexible rule A typical calibration relationship is presented in Figure 2.9. All data points should be within £2 percent of the curve of best fit 13. Should the rotameter be used in a field location where the barometric pressure and/or temperature is different than those Conditions when the rotameter was. calibrated, the following corrections must be applied to convert the flow rate to standard conditions. This correction factor 1s not advisable for conditions that differ greatly from those at which the rotameter was calibrated Greater accuracy can be ‘obtained by developing calibration Surge Tonk at Motime: (025-05 Lners) { Pimp” L —_— Rotameter calibration ooparatus.Section 2.1.2 Jan, 1983 ‘uuo} e1ep vonerqye: noweroy ezemey =e wa (gS) neta, Qa0/ Ob'zt On! ot _ ace | ol6 goo/ Ob't Oe ___ [007 BE a ___] OOS : Pb zi Sst | S'S3h\ 00s tb! Shi i 00S sli o 00s 13° 6 ~~) Bees | S88 00S ISL az | 2 _ | 0S 132 | “ a Oo7 2H 2 + eee | tee “OOF pi 377 3 oor | plT > ee ee = oor | pearl /icae é . ' oo7 227 LLE z Se 116 oa ae : Mees “ee ct pases wun ‘oun tel one. vumen | ate aeuecttinp site | 8 Tee EL tui ray ORB drives waen Byun Frog sm yee ke 3S i es Oa arg Yost Jo}oweoySection 2.1.2 10 Jan, 1983 Table. Temp, °C. Density, g/mt Temp, 2 Absolute Density of Water Walues numerically equal to absolute density of H:0) 2C____ Density g/ml 25 0.99707 26 0.99681 27 0.99654 28 0.99626 29 0.99597 30 0.99567 31 0.99637 32 0.99605 33 0.99473 4 0.99440 Flow Meter Seria! No. _J4729 Temperature (°C) fimon recur Colbrued by Dee Braid [| {| {| j | j {| | | os 1042 {a STP (Qu), min 4618 r= flow rate at field conditions from calibration curve, ml/min yaromettic pressure at field ‘conditions, mm Hg 20 T= temperature at field conditions, 16 0.99913 16 0.99887 7 0.99880 18 0.99862 19 0.99843 20 0.99823, 2 0.99802 22 0.99780 23 0.99756 24 0.99732 300} 250}— 200}— 3 g i 150)— 2 100}-— so}— / ° 0 02 04 06 Flow. Figure 2.9 Typical rotameter calibration curve, ‘curves for expected conditions. Q,= 0, (_Pr_x298)"* 760 Tr Equation where a flow rate corrected to standard ‘conditions from field conditions, ml/min 2-10 Control Devices ‘The rotameters and needle valves (short-term sampling only) or the critical orifices used as flow-contro! devices in the SOz sampling trains should be checked for the appropri range of sampling rates, but they do not require strict calibration because their values cannot be used to determine the sample volume. The sample volume is determined from the sampling time and the sample flow rate measured before and after sampling by use of a flow measurement device connected to the inlet of the absorber. Flow rate requirements for different ‘sampling periods and typical hypodermic needle sizes that will give these flow rates are: 1. 30 minutes of sampling at 0.9 to 1.1 liters/min. Use a 1-inch 22-gauge hypodermic needle. 2. One hour of sampling at 450 10 ‘860 cm?/min. Use a 5/8-inch, 23- ‘gauge. hypodermic needle, 3. 24-hours of sampling at 180 to 220 cm?/min Use a 3/8-inch 27- ‘gauge, hypodermic needle. In the short-term sampling train only, a rotameter and needle valve covering the appropriate range may be used. The flow control devices in the assembled sampling train should be checked to ensure that the appropriate range can be obtained before they are takon into the field. Any needle unable to give the accepted range should be discarded The flow rates are checked by use of the procedures described for determining the flow rates before and after sampling in Section 2.1.4, Subsection 4 4, Constant flow rates through hypodermic needles can be achieved ‘only when critical flow conditions are ‘met, These conditions exist when the absolute pressure downstream of the needle (P,) is <0.45" of the absolute pressure upstream of the needle (Pu)that is, when Py =0.45 P,, For the $02 sampling trains, the upstream pressure (P,) is usually 25 mm (1.0 in.) Hg less than the barometric pressure, and the downstream pressure (Ps) is equal to the barometric pressure minus the pressure from the vacuum gauge (Ps) Since the barometric pressure decreases with altitude, the critical flow conditions are satisfied at lower vacuum gauge readings at higher altitudes. Vacuum gauge readings for critical lows at several altitudes a shown in Table 2.3. A minimum safety ce 8 ofthe Reference Method, Section 21 Tie verdes the 045 for uve with the frypadermic nase Reference 0! Section P12 gwos 053 a8 a purely theoretical valve.Jan. 1983 u Section 2.1.2 Table2.3 Vacuum Gauge Readings to Achieve Critical Flow for Various Elections (Assumed pressure drop across sampling train = 25 mm (1.0 in.J Hal Elevation Standard Gauge reading above sea level barometric pressure for critical flow fmm Hg in. Hg mm Ha inHg o 0 760 29.9 429 169 305 1000 732 288 414 163 610 2000 706 278 399 157 915 3000 680 268 385 152 1220 4000 656 258 146 1626 5000 632 249 14.1 1830 ‘6000 6039 13.6 factor of 20 percent of the g reading should be added to the table values to ensure critical flow during the total sampling period Flow rates through hypodermic needles used as critical orifices are directly affected by upstream pressures, which are in turn affected by barometric pressures. Care must be exercised when needies are used at elevations that differ greatly from that at which they were checked. 2.3. Calibration of Analytical Balance The balance calibration should be verted when tre balance is (1 frst Ou (2} any time it is moved or [subjected to rough handling, and (3) during routine operations when a standard weight cannot be weighed within £0.5 mg of its stated weight. If at any time, one or more of the standard weights cannot be measured within +0.5 mg of its stated value, the manufacturer should be asked to recalibrate and adjust the balance. The results of all balance checks shauld be recorded in the log (Figure 2.10) 2.4 Calibration of Elapsed- Time Meter The elapsed-time meter {synchronous motor, type 60 H2} should be checked on site or in the laboratory every 6 mo against a timepiece of known accuracy, If the indicator shows any signs of being temperature-sensitive, it should be checked on site during each season of the year; a gain or loss of more than 2 min in a 24-h period warrants an adjustment or replacement of the indicator. Results of these checks should be recorded in the calibration log. 2.5 Calibration of On-Off Timer The on-off timer should be calibrated and adjusted by using an already-calibrated elapsed-time meter as the reference. The calibration procedure should be performed ‘quarterly, and the calibration data ‘should be recorded in the timer log (See Figure 2.11 for an example and Section 2.1 13 for a blank form.) An example calibration procedure is presented below.‘ Figure 2.12 is a wiring diagram for the calibration 1. Plug a correctly wired timer into an electrical outlet 2. Set the timer to the correct time, 3. Set the on and the off ume tippers for the 24 h. 4. Plug the test light into one of the output plugs, and plug an elapsed time meter into the other 5. Check the system by manually operating the switch on and off. 6. Allow the system to operate for the 24-h period, and determine the ‘elapsed time from the elapsed-time meter. if the elapsed time is 24h +16 mun, the timer 1s acceptable for field use, if not, adjust the tripper switches, ‘and repest the test.Section 2.1.2 2 Jan. 1983, Analyucal Balance Quality Contro! Lag Date ____Tume Technician y29774 1107 asm ¥/a9/74 1308 one ‘129/74 240. DEK #03 Saree rave | 357 ee Yarn | bee aie | te bee anne | ee air | 5a | _OEK e774 aes EK Bers 1008 bee B78 | me bee B78 1292 } DEK 8/1/74 | 143, | ‘DEK ata 24 bee age 5% bee e778 Ts] DEK fer | S66 ork ao78 1089 Bex a7 | Bie bee a7 738 ee 8/2/74 | 303 EK sere | 300 bee e797 8/3074 zl aoe e578 e/s/74 ear7e 5/3/74 ear e774 ear Bee a76/74 eK arr bee e674 Bex eer oer ser bee aera Bee a77/74 ee B78 bee errr oer B74 bee B78 oor 20000 ber ararra 7.0000 $0000 DER e247 e001 — 20001 orn e287 0007 200oT ee Figuie2.10 Example of an analytical balance pertormance record,13 Section 2.1.2 Jan. 1983 y0 oyausexy —-44'z0unb ig OTT | She VRE Dowoma [ia] Yay | Tee, TFA aT | 7 i ep ae | es eieg aSection 2.1.2 1“ Jon. 1983 (00-01 Timer [618 min/24 hy Indicator Lamp Figure 2.12 Diagram of a tier calibration system. Table2.4 Activity Matrix for Calibration of Equipment Elepsed:Time Meter (92. min/24 bi load Action it Frequency and method requirements Equipment Acceptance linuts of measurement are not met Wet-test meter % error =1% (Fig 2 2) Check upon receipt and Adjust by manufacturer's quarterly with liquid Instructions, or return to positive displacement ‘manufacturer. (Subsec 2.1.1) Soap-bubble meter % error <1% (Fig 2.4) Calibrate upon receipt from As above ‘manufacturer with gravi- metric displacement (Subsec 2.1.2) Mass-Hlow meter All data points within +2% Calibrate quarterly with As above of best-fit curve bubble or wet test meter (Subsec 2.1.3) Rotameter As above Calibrate quarterly with As above bubble meter (Subsec. 21.4) Flow control devices, rota Appropriate range for Check flow rate initially Clean or replace rotam- meter and needle value or ‘sampling period: rotameter, and before and alter each eter: discard hypodermic hypodermic needles 450 to 1100 erm2/min; ‘sampling period with cali- needles. orifices, 900 t0 1100 cm?/ brated flow measuring ‘min, 30-min sampling. 450 device. t0 550 cm?/min, 1- to 3. ‘hour sampling, 180 to 220 em?/min, 24-hour ‘sampling Analytical Standard weights +0.6mg Verity calibration when ‘Repeat check to verity balance of stated values first purchased, after ‘malfunction: have men- ‘moving or rough handling, _ufacturer recalibrate and and when a standard adjust as needed weight is not within 40.5 ng of stated value. Elopsed-time meter 22 min/24h Check every 6 mo with Adjust or replace. timepiece of known accuracy. On-off timer £15 min/24h Use calibrated elapsed- Adjust the tipper switches; time meter quarterly ‘repeat test (Subsec 2.4).Jan, 1983 1 Section 2.1.3, 3.0 Preparation of Reagents The quality control functions for preparation of reagents a ‘summarized in Table 3.1 at the end of this section. 3.1 Distilled Water The standard specification for reagent water is described in the ASTM designation D 1193-72; this document requires the Type-lI grade of water, which is prepared by use of 2 still designed to produce a distillate having a conductivity of <1.0 mieromho/ em at 25°C (77°F) and 9 BH range of 6.6 to 7.2. ‘The following purity test should be performed after each lot of water Feagent is prepared if the slope and intercept of the standard curve fail to meet the specified criteria (Section 218). 1, Add 0.20 mi of a potassium permanganate (KMn04) solution (0.316 g KMnO4/liter) to a mixture of 500 ml of distilled water and 1 mi of sulfuric acid (HSO4) in a stoppered bottle made of chemically resistant glass. If the KMnO« color (pink) does ‘hot disappear completely after standing for 1 h at room temperature, the water is suitable for use; if the color disappears, the water must be purified 2. Wai ils the purity test con be purified as follows 2. Add 1 9 each of KMnO« and barium hydroxide (BaOH) for each liter of distilled water. b. Redistil the water in an all-glass sii. ©. Perform the test for purty sescribed above 3. Repeat both the purification procedure and the test for purity until the slope and the intercept of the standard curve meet the specified limits, 4. Store the reagent water in an inert container with a vent guard. (A suitable guard isa drying tube filled with equal parts 8-20 mesh soda lime, oxalic acid, and 4-8 mesh calcium chloride separated from each other by a glass-wool plug.) Replace the vent guard drying materials every 30 days. 3.2, Absorbing Reagent 3.2.1 Reagent Preparation - The 0.04M potassium tetrachloromercu- rate (TCM) absorbing reagent should be prepared according to the following procedure, 1. Dissolve 10.86 g of mercuric chloride, 0.086 g EDTA (ethylenediaminetetraacetic acid disodium salt) and 6.0 g of potassium chloride in distilled water, and dilute to 1 liter. Usually it is necessary to prepare larger quantities of the absorbing reagent to meet the sampling requirements of the agency. Warning: The reagent 1s highly poisonous. Rubber gloves should be worn when preparing the absorbing reagent. If spilled on the skin, it must be flushed off with water immediately. 2, Label the reagent bottle, and include the date of preparation. 3.2.2 Reagent pH Test - For each lot of absorbing reagent prepared for sampling, the following pH test. procedure should be conducted 1, Standardize the pH meter with buffer solutions of pH 4.0 and pH 7.0 2. Measure the pH of the absorbing reagent. The optimal pH is 4.0. 3. Discard the reagent if the pH 1s. <3.0 or >5.0. Dispose of the absorbing solution according to one of the disposal techniques described in Section 2.1.5, Subsection 5.5 3.2.3 Reagent Storage - The absorbing reagent should be stored in 2 toppered container, and the reagent should be discarded if it is >6 mo old (normally stable for 6 mo). it should be visually examined before each use and discarded if @ precipitate is visible. The absorbing solution should be discarded in accordance with ane of the disposal techniques described in Section 2.1.5, Subsection 5.6 3.3. Sulfamic Acid (0.6%) Sulfamic acid (0.6 9) should be dissolved in a 100-mi volumetne flask with water and diluted to the 100-ml ‘mark, The solution should be kept in @ glass- stoppered flask while not in Use, and it should be prepared fresh daily 3.4 Formaldehyde (0.2%) Five milliliters (5 mi) of formaldehyde solution (36-38%) should be diluted to 1000 mi with distilled water. The 0.2% solution should be kept in ‘stopped container while not in use, and it should be prepared fresh daily 3.5 Starch Indicator Solution A starch solution for iodimetric determinations should be prepared by following these three steps: 1. Triturate 0.4 g of soluble starch and 0.002 g mercuric iodide (oreservative) with a small amount of water to form a paste, 2. Add the paste slowly to 200 mi of boing water, and continue the boiling unti! the solution is clear. 3. Allow to cool, and transfer to a glass-stoppered bottle. Alternatively, a solution of stabilized starch for iodimetric determinations can be purchased commercially 3.6 Stock lodine Solution (0.1N) The procedure for preparing the 0.1 'N todine solution 1s as follows, 1. Place 12.7 g of iodine in a 250-mi beaker. 2. Add 40 g of potassium iodide (ki) and 25 ml of water to the beaker. 3. Stir until dissolved 4. Transfer the contents of the beaker to 2 1000-m! flask, and dilute to the mark with distilled water. Keep the stock solution in a glass-stoppered dark bottle, and store in a cool place. 3.7. Working lodine Solution (0.01N) The approximately 0.01N iodine solution should be prepared by diluting 50 ml of the 0.1N stock solution to 500 mi with distilled water. The 0.01N working solution should be kept in a glass-stoppered dark bottle or dark flask, and it should be prepared fresh daily. 3.8 Hydrochloric Acid (1N) The solution of 1N HCI should be prepared by slowly adding 86 ml of Concentrated HC! (12N) to 500 mi of distilled water. After it has been allowed to cool, it should be diluted to 1000 mi with distilled water. 3.9 Stock Sodium Thiosulfate Solution (0.1N) A..1N stock solution should be prepared by dissolving 25 g of sodium thiosulfate (NazSz03 - 20) in 100 mi of freshiy boiled but cooled distil water and by adding 0.1 g of sodium Carbonate ta the solution. The solutionJan. 1983 should be allowed to stand 1 day before standardizing, The procedure for standardizing against a potassium iodate (KIO3) standard before each use is as follows: 1. Dry ACS reagent grade KIOs at 180°C (356°F) for 3 hin a drying 2. Cool the dried KIOs in a desiccator. ‘3. Weigh and record the weight 10 the nearest 0.1 mg of the 15 9 of the dried cooled KIOs. 4, Add the weighed sample of KIO t0 9 §00-ml volumetric flask, and dilute to the 500-ml mark 5. Pipette 50 mi of the KIO: solution into a 00-m flask: add 29 of KI and 10 ml of 1N hydrochloric acid (HCI), 6. Stopper the flask and wait § min before titrating to a pale yellow with the 0.1N stock thiosulfate solution, 7, Add 5 mi of a starch indicator solution, and continue the titration until the blue color disappears. 8. Calculate the normality (N,) by using the following equation. Ns=Wx2.80 M Equation 3-1 where Ny= normality of stock thiosulfate solution We weight of KIOa. g folume of thiosulfate required, 0.1 (KiOs fraction used)x 10° (convert g to mg). 36,67 (equivalent weight of KIOs) Store the 0.1N sodium thiosulfate ‘stock solution in a glass-stoppered flask, 3.10 Sodium Thiosulfate Titrant (0.01N) The 0.1N stock thiosulfate solution (100 mi) should be accurately pipetted into a 1000-ml volumetric flask and diluted to the mark with freshly boiled but cooled distilled water. This 0.01N solution is not stable, and must be prepared fresh daily from the stock thiosulfate solution. It should be kept in a glass-stoppered flask or bottle when not in use. The normality of the sodium thiosulfate titrant (Nx) should be calculated as follows: Nr= Ns x 0.100 Equation 3-2 3.11 Standard Sulfite-TCM Solution This solution is prepared by digsolving 0.30 g of sodium 2.80= metabisulfite (Naz620s) oF 0.40 9 of sodium sulfite (NazSOs) in 500 ml of freshly boiled but cooled distilled water. (Because sulfite solution is unstable, water of the highest purity should be used to minimize the instability.) This solution contains the equivalent of 320 to 400 ug SO2/mit; the actual concentration is determined by adding excess iodine and by back- titrating with the .01N standard Sodium thiosulfate solution. The working sulfite-absorbing reagent solution (see Subsection 3.12) should be prepared while the iodine solution is being added to the flasks, The procedure for standardizing the sulfite solution is as follows: 1. Label each of three 500-mt flasks with an A, and label three other flasks with a 8. 2. Pipette 60 mi of the 0.01 ‘working iodine solution into each of the six labelled 600-mi flasks. 3. To each A flask (blank), add 25 imi of distilled water; to each B flask (sample), pipette 25 ml of the standard sulfite solution. 4. Stopper the flasks, and allow the Solutions to react for 5 min. '6. Use a 80-ml burette containing standardized 0.01N throsulfate to titrate each flask to a pale yellow. 6, Add 5 mi of starch solution to ach flask, and shake thoroughly; continue the titration until the blue color disappears. ‘Store the standardized sulfite-TCM folution in a glass-stonpered bottle or lask 3.12 Working Sulfite-TCM Solution A quantity of § ml of the standard solution (prepared above) should be pipetted into @ 250-mi volumetric flask, and diluted to the mark with 0.04M absorbing reagent. The SOz Concentration in the working solution should be calculated by using the dat in Subsection 3.10, as follows: sn s0vni- (20094882) s0.02 af Equation 3-3, where A and B are averages of the three replicate titrations, and ‘32,000 milliequivalent weight of S02. ug A= volume of thiosulfate needed for the blank, mt B= volume of thiosulfate for the sample, mi Nr= normality of thiosulfate ‘titrant 0.02 dilution factor 25= vol. of standard sulfite solution, ml This solution is stable for 30 days at 5°C (41°F) if refrigerated, If not kept at 5°C, it should be prepared fresh daily, 3.13 Pararosaniline Stock Solution Harleco Co. offers high purity pararosaniline (PRA) dye that can be Used without purification for the preparation of the standard curve (described in Subsection 5.2) f the slope, the intercept, and wavelength ‘of maximum absorbance are within ‘specifications. if the specifications are not met, the dye must be purified 3.13.1 Dye Specifications - Dye Specifications are as follows: 1. The dye must have a maximum ‘absorbance at a wavelength of 540 nm when assayed in a buffered solution of 0.1M sodium acetate acetic acid, 2. The absorbance of the reagent blank, which is temperature-sensitive (0.018 absorbance unit/°C), must not exceed 0.170 at 22°C with a t-cm optical path length when the blank is prepared according to the specified procedure. 3, The calibration curve (Subsection 5.2} must have a slope equal to 0.030 30.002 absorbance unit/ug SOz with 2 1-cm optical path length when the dye is pure and the sulfite solution is properly standardized 3.13.2. Purification Procedure for PRA ~ The following purification procedure is given in the event that the PRA does not meet the specifications. 1. Place 100 mi each of 1-butanol ‘and 1N HCl in a 250-ml separatory funnel, shake, and allow to equilibrate. Note: Certain batches of butanol contain oxidants that create ‘an $02 demand. Check before using by placing 20 mi of 1-butanol and 5 ml of 20 percent KI in a 50-ml separatory funnel and shaking thoroughly. If a yellow color appears in the alcohol phase, either redistll the 1-butanol from the silver oxide and collect the middle fraction, or purchase @ new supply of 1-butanol. 2. Weigh 100 mg of pararosaniline hydrochloride in a small beaker; add 10 it 60 mi of the equilibrated acid (drained from the bottom of the Separatory funnel in Step 1); and then let the mixture of PRA and acid stand for several minutes. butanol (drawn from the top of the separatory funnel in Step 1), transfer to the funnel the acid solutionJan, 1983 Section 2.1.3, containing the dye, and then extract The violet impurity will transfer to the organic phase (top layer). 4. Transfer the lower aqueous phase from the separatory funnel into another separatory funnel, add 20 ml of 1-butanol, and extract again, Repeat the extraction procedure in Step 4 with three more 10-mi portions of T-butanol This procedure Usually removes most of the violet impurity that contributes to the blank, but the extracted phase (bottom) will Still be red. 5. After the final extraction, filter the acid (bottom) phase through a cotton plug into 2 50-ml volumetric flask, and dilute to the mark with 1N HCI. This PRA stock reagent will be yellowish red 3.13.3. Assay of Pararosaniline ‘Stock Solution The following assay should be performed after each reparation or purchase of a new lot of PRA, 1. To prepare a butfer stock solution with a pH of 4.79, dissolve 13.61 g of sodium acetate trihydrate 1 distilled water in a 100-mt volumetric flask, add 5.70 ml of glacial acetic acid, and dilute to the mark with water. 2. Dilute 1 mi of the purified PRA stock solution (Subsection 3.13.2) 10 the mark in @ 100-ml volumettic flask with distilled water. 3, Transfer a 5-ml aliquot to a 50- mi volumetric flask: add 5 ml of the acetate acetic acid butter solution (from Step 1); and dilute the mixture to the mark with distilled water. Let the mixture stand for 1h. 4, Measure the absorbance at 540 ‘am with a spectrophotometer. Compute the percent purity of the PRA se PRA = AK, W Equation 3-4 where. SPRA= PRA purity, % ‘A= measured absorbance of ‘the final mixture, absorbance units. = conversion factor value (molar absorptivity), dependent on quality of spectrophotometer and associated equipment? (e.g.. em cuvettes and a spectral band width half intensity of 11 nm, K = 21.3); Note: If these specifications are not met, the dye analysis will be incorrect; W= weight of dye in 80 ml of PRA stock solution, 9 (e.g. 100 mg is used to prepare 50 ml in the purification it procedure, W = 0.100 9; and 10.5 q is used to prepare 250 mi, W 1s still 0.1003; When obtained from ‘commercial sources, use the stated concentration to compute W; for 0.20 percent concentration of 98 percent purity PRA, W = 0.098 g per 50 mi. 6. Record the results of the assay in a ealibration log, 3.14 Pararosaniline Reagent The procedure for preparing a pararosaniline reagent is as follows: 1. To a 250-ml volumetric flask, ‘add 20 mi of PRA stock solution 2. ‘Add an additional 0.2 ml of stock solution for each percentage that the stock assayed below 100 percent. 3. Add 25 mi of 3M phosphoric acid, Dilute to the 250-m mark with distiled water. This reagent, stored in a glass- bottle, is stable for at leastSection 2.1.3 sant Table 3.1 Activity Matrix for Preparation of Reagents Reagent Distilled water Water storage Absorbing reagent pH test Absorber reagent storage Sulfamie acid Formaldehyde ‘Starch indicator solution ‘Stock iodine solution Working iodine solution Hydrochloric acid ‘Stock sodium thiosulfate Sodium thiosulfate titrant Standard sulfite-TCM solution Working sulfite-TCM solution Stock pararosaniline solution PRA reagent —_Acceptonce limits ‘Kind. color ipink) persists atter 1h at room emperoture Inert container with vent guard 3.0

25 h. The actual sampling period must be known to within +15, min (see Section 2.1 2) 4.3.4. Sample Handling - The procedure for sample handling is a5 follows: 1. First remove the accordion tubing (color-coded) from the absorber impinger tube. 2. For 24-n samples, estimate the volume of absorber reagent remaining in the absorber flask after sampling, mark the TCM level n the absorber with tape oF some other easily removable indicator, and record the estimate on the sample record form. To assist in this estimation, mark the tubes at the 35- and 50-ml levels with a marking pen. If <35 ml of sampling reagent remains after sampling, void the sample, and indicate this on the form. If 50 ml of sampling reagent mains after sampling, state (under Remarks” on the sample record form) that no evaporation occurred during the sampling. 3. If there 1s evidence of malfunction (¢ g, absorbing reagent forced out of absorber into the vacuum system), record this on the sample record form Normally, the sample 1s invalid under this circumstance 4. Place the tube caps first on the impinger tube (color coded) of the absorber and then on the suction tube Press caps firmly in place. and place the absorber in the shipping block, Note: For 30-min and 1-h samples collected in glass impingers, shake the absorber thoroughly. quantitatively transtar all of the ‘exposed reagent to a test tube or small bottle with a Teflon-tined threaded cap, and place the sample in the shipping block 5 Record on the sample record form any pertinent observations relative to sources, weatherSection 2.1.4 6 Jan, 1983 Gas Bubbler Data Record pen Clamp 248 240 248 ‘Station Location Vacuum Reading Start Cay @ State Vacuum Resting End Ste & Adress se TS mo fay 51 mn Project SMELTER site no SZ ‘Stop Semping 6 6 BI 23 67. mmo dey wr = Pollutant Elapsed Time Start SO, Sompler 10 No, — 22 Type of Flow Measuring Device Identification Number of Device Inival Flow 204 rain a veo 205 enl/onin— semoie no, 471 __ —_ROTAMETER ‘Nonunol Flow Rate Final Flow 2OB ml/min» aiterence LO Average Average sample temperature ZO °c Retawve humeity 5090 Ambvent temperature: Start — Barometric pressure. Start —_mm Hg. Stop REMARKS: : °C, Stop — "C, Average 25. 2c _ mm Ha, avera90 AVL Ome Hg ‘Meteorological conditions for use when anomaly occurs Elapsed Tune Stop L437 mn Sample collected within ‘guidelines gwen below WIND calm taht —— gusty wisiiiry clear hary sky Z. clear scatered overcast HUMIDITY dry moderate humid rainy TEMP °F <20___ 20-40 41-60 “61.80 >90, Gudennes Proper How rate —1/2:h samples - 900-1100 em?/mn 1h samples 24h samples "450-550 em'/min 180.220 emn/min 24: sampling ~ 23 h < samphng time < 25h |= 335 mi of absorbing reagent — sampler timer accuracy #15 ‘Sample record form. Figure 4.10. conditions, etc., that might affect the S02 level 6. Complete the sample record form in duplicate, return the original copy with the absorber in the shipping ‘block, and file the duplicate in the site log book. 7. If samples must be stored before shipment for analysis, store them in a refrigerator or cooler at 6°C (41°F). A shipping container that can maintain, 2 temperature of 5° +5°C is used to transport the sample from the collection site to the analyti laboratory. Ice coolers or refrigerated shipping containers have been found ‘remain atter sampling ‘min’26 to be satisfactory. The use of eutectic cold packs instead of ice will provide a better temperature control. Such equipment is commercially available from Cole-Parmer Company, 7425 North Oak Park Avena, Chicago, Minois 60848, 4.4 Determination of the Flow Rate of SO2 Sampling Trains ‘The SO2 sampling train that is used {for short-term periods of 30 minutes. and 1 hour normally has one of two flow control systems. One system has 2 needle valve and indicates the flow with a rotameter. The other uses various sizes of stainless steo! hypodermic needles to control the flow. The 24-h sampling trains also use staini | hypodermic needles to the flow. For short- mpl indard flow rate is determined at the sampling site at the initiation and completion of sample collection by use of a calibrated flow-measuring device connected to the inlet of the absorber. For 24-hour samples, the standard flow rate is determined at the time the absorber is placed in the sampling train and again when the absorber isJan. 1983 Section 2.1.4 moved from the train for shipment to the analytical laboratory. A librated flow-measuring device connected to the inlet of the sampling train is used for this purpose. The flow rate determination must be made with all components of the sampling system in operation (e.g., th absorber temperature controller and any sample box heaters must be operating). 4.4.1 Flow Rate Measurement - ‘Three step-by-step procedures for ‘measuring the sampling flow rates are presented here, They involve the use of a mass-flow meter, a rotameter, or a soap-bubble meter. The reference method requires that the flow rate of each SOz sampling train be measured before and after each sampling period. The initial and final flow rates must agree within +5 Percent or the sample is voided. Therefore, itis very important that the flow-measuring device selected have ‘the appropriate range, accuracy, and readability to meet this specification. The typical flow rates for 30-min, 1 hour, and 24-hour samples are 1000, 500, ‘and 200 ml/min, respectively The range of a mass-flow meter sed as a flow measuring device hould be such that the measured flow is between 50 and 90 percent of full scale Regardless of the range, the mass-flow meter must have @ readability and reproducibility of 1 percent of the measured flow to ensure that only samples from trains whose flow rate did change by more than 5 percent are invalidated. Mass- flow meters should be calibrated according to procedures given in Subsection 2.1.3, Rotameters used as flow measuring devices should have a minimum scale of 6-in. (150 mm) with no less than 100 divisions The measured flow should be between 50 and 90 percent Of full scale, If these conditions are met, only samples from the trains whose flow rate did change by more than 5 percent should be invalidated Rotameters should be calibrated according to procedures presented in ‘Subsection 2.1.4 Bubble meters should be of a size that the volume is displaced in 10 to 30 seconds during the flow ‘measurement. Bubble meters are calibrated according to procedures resented in Subsection 2 1.2 When flow measurements are made y inserting @ mass-flow meter or rotameter Between the probe and the absorber, the tume required for the initial and final flow measurements should be included in the total sampling time, Bubble meters are not as easily ingerted between the probe and absorber inlet, and the solution in the bubble meter will absorb at least some of the SO.. Therefore, the time required to do the initial and final flow measurements should not be included in the sampling time, and a charcoal scrubber should be Inserted between the bubble meter and the absorber to. ensure the removal of SOs. Care must be exercised in the selection of the charcoal tube so that the pressure drop across the sampling system will not be increased enough to alter the sampling rate. 4.4.2. With a Mass Flow Meter - The following procedure should be used to measure the flow before and after sampling. 1, Assemble the equipment for sampling, as shown in Figure 4.11 2. Be Sure all connections are tight. 3, Be sure the absorber inlet line is connected to the mass-flow meter transducer outlet, 4, Zero the mass-flow meter, 5. Turn the vacuum pump on and adjust the needle valve to obtain approximately the desired flow (prior to sampling only). Record the vacuum reading on the sheet 6. Check for bubbles in the sampling tube. Plug the inlet of the mass-flow meter, and check for zero flow on the rotameters. If a zer0 flow Js not obtained, check for leaks. Unplug the inlet 7. Read the flow rate on the mass- flow meter after the meter indicator has stabilized (about 30 s) and shut off the pump. &. Turn the pump on, and repeat Step 7 two more times. 9. Average the three flow rates. 4.6.3, With a Rotameter - The following procedure should be used to measure the flow before and after sampling 1. Assemble the equipment, ‘shown in Figure 4.12. 2. Place a new rubber septum on the tube (prior 10 sampling only). 3. Be sure all connections are tight '4. Be sure the line from the surge tank outlet is connected to the inlet of the sampling tube absorber. 5 Turn the vacuum pump on, and ccheck the vacuum by placing a finger ‘over the end of the vacuum line. (The ‘vacuum gauge should read at least 530 mm (21 in.) Hg at a barometric pressure of 760 mm (29.92 in), Turn the vacuum pump off. 6. Insert a needle through the center of the septum, perpendicular to the plane of the septum face. 7. Turn the vacuum pump on. Slide the needle holder snugly into the recess at the base of the needle, and ccheck for bubbles in the sampling tube. Plug the inlet to the rotameter land check to see that bubbling ceases in the absorber. if bubbling persists, check for leaks. Unplug the inlet. 8. Read the ball position on the rotameter; record the flow rate corrected to STP, 760 mm {29.92 in.) Hg and 25°C (77°F), from the rotameter calibration curve; and read the vacuum gauge to make sure the vacuum is sufficient during the flow measurement 9. Repeat Step 8 two more times. Turn pump off and then back on after each run. 10. Record the ambient temperature and pressure oF obtain the average for the sampling period from the local ‘weather bureau. 11, Average the flow rates of the three runs, 12. If the rotameter is used in a field location where the barometric pressure and/or temperature is which the rotameter was calibrated, apply the following corrections to convert the flow rate to standard conditions. This correction factor is not advisable for conditions that differ ‘greatly from those ich th Fotameter was calibrated, Greater accuracy can be obtained by developing calibration curves for expected conditions. =a, ee 760 Ty Equation 4-1 where ,= flow rate corrected to standard conditions from field conditions, m/min i= flow rate at field conditions ‘from calibration curve, ml/min P,= barometric pressure at field conditions, mm Hg T= temperature at field conditions, °K 4.4.4 With a Bubble Meter - The following procedure should be used to measure the flow before and after the sampling, 1. Assemble the equipment for sampling, as shown in Figure 4.13, 2. Place a new rubber septum on the sampling tube only prior 10 sampling, 3, Be sure all connect 2 10 tightSection 2.1.4 a Jan. 1983 ro Probe = ‘Mass Flow meter i0 ous 30 mi 20 mi 10m ‘Note: Rotameter and needle valve can bbe replaced with appropriately sized hypodermic needle (Section 2.1.11] Needle Rotameter Glass woo! or Silica Get — diosy "Ora, amma — Note A midget mpinger 18 sed for T-hour sampling Figur 12 4, Be sure the charcoal tube is connected between the bubble meter and the inlet of the sampling tube impinger. 5. Turn the vacuum pump on and ccheck the vacuum by placing a finger ‘over the end of the vacuum line, (The vacuum gauge should read at least 530 mm (21 in) Hg at a barometric pressure of 760 mm (29.92 in) Hg. Turn the pump off 6. Insert a needle through the center of the septum, perpendicular to the plane of the septum face. 7. Turn the vacuurn pump on, 8. Slide the needle holder snugly into the recess at the base of the needle, and check for bubbles in the Absorber for 24n Sampling Determination of Hw rate of long-term sompling trein using @ rotometer. sampling tube. Plug the inlet to the bubble meter and check to see that, bubbling ceases in the absorber. If bubbling persists, check for leaks. Unplug the intet. 9, Touch the surface of the soay solution with the open end of the bubble meter so that a soap bubble will start to travel up the bubble meter tube. Repeat several times or until the bubble travels the full length of tube without breaking 10. Touch the surface of the soap solution with the open end of bubble meter so that a single bubble starts to travel up the bubble tube. When the bubble passes the first line of the ‘graduated scale, start the stopwatch ‘and record the time and volume displaced, Read the vacuum gauge to make sure the vacuum is sufficient during flow measurement, 11. Repeat Step 10 two more times. Record the time and the volume each time, 12, Record the ambient temperature and pressure, or obtain the average for the sampling period from the local weather bureau. 13, Average the times and volume displacements for the three runs. 14, Divide the average volume displacement by the average time to determine the flow rate.Jan. 1983 9 Section 2.1.4 un. Tube e 6-10 Mesh Polypropylene 2-Port Tube Closure Membrane Filter Bubble Meter Absorber for 24h Sampling Figure 4.13 18. Correct the average flow rate 10 standard conditions of 760 mm (29.92 in.) Hg and 25°C (77°F), using Equation 4-2. Qs = Quer x Pe {1-BHIPi0 Pasa 298.16 (Tate: * 273.16) Equation 4-2" wher ‘Qay= flow rate at standard ‘conditions, std liters/min (25°C and’760 mm Hg) Qac:= flow rate at monitoring sit ‘conditions, liters/min jarometric pressure at monitoring site conditions , mm or in. Hg fractional relative humility of the air being measured; determined with a sling psychrometer or similar evice, oF obtained from the local weather station. apor pressure of water at the temperature of the air in the flow or volume standard, in the same units as Ps (for ‘wet volume standards only, ‘.e., bubble flowmeter of wet test meter, see Section 2.1.2: for dry standards. barometric pressure, in the same units as P, (760 mm Hg or 29.92 in, Ha) Pro: Tram= temperature of the air in the ‘flow or volume standard, °C {e.g., bubble flowmeter) Ha barometer is not available, the following equation may be used to determine an average barometric pressure: Px = 760-.076(H) mm Hg or Pe 29,92-.0030(H) in. Hg Equation 4-3 where H = sampling site elevation above sea level in meters. 4.5 Flow Rate Validation .6.1 Initial Flow Rate I the flow meter or the hypodermic needle in the sampling train has been calibrated, the initial flow rate (determined by ‘one of the flow-measuring devices listed in Subsection 4.4) should be compared with the rate of the flow- controlling device to determine if the train is leak-free. If the initial flow rate (Q,) differs from the flow rate of the critical orifice or the flow rate indicated by the flowmeter in the sampling train (Qc) by more than 5 percent (as determined by Equation 4-4), checks for leaks should be made and the O, should be determined % Diff -Q-Qe x10 Qe. Equation 4-4 Hypodermc Needle Determination of flow rate of long-term sampling train using soap-bubble meter 4.8.2 Final Flow Rate The initial flow rate and the final flow rate must agree within +5 percent for a valid ‘sample to be collected. This check should be performed in the field when the final flow measurement is made 0 that any discrepancies can be determined at that time. Immediate ‘onsite determination of the reasons {for variable flow rates can prevent further data loss. The sample should be invalidated if the difference between the initial (Q,) and final (Qi) flow rates is more than 5 percent as determined by Equation 45, Q1x100 a 96 Diff =O. Equation 4-5Section 2.1.4 10 Jan. 1983 Table4.1 Activity Matrix for Sarmpling Procedure Action it Frequency and method uicements Activity Acceptance limits ‘of measurement are not met Absorber selection 1) Short-term, <3 h; Visually check each ‘Select proper absorber 30-mi all-glass midget sample. impinger 2) 24-h sample: poly propylene tube and closure with glass impinger tube 3) Orttice 1D >#79 drill ‘and <178 drill | Cleaning absorber Clean absorber Water and acid bath prior | Clean it (0 each use Dispensing TOM 1) Short-term period, 10 | Visually check each Correct the discrepancy miTCM sample. 2) 24-h period, 60 mi TCM Assembly of absorber As diagrammed Visually check Reassemble. Determination of flow rates | Percent difference <5% | Calibrated flow measuring | Void sample. before and after sampling device (Sec. 2.1.2) ‘Sample 10 All required information | Visually check Complete the stick-on Tabel/ Packing for shipment Shipped in insulated coo!- | As above Repack as appropriate. pack container ‘Sampler assembly, 24-h 'NASN specifications (Figs | As above Reassemble if necessary. bubbler 46,47, 48) Installation of absorber and | See Subsec. 4.2.6 and As above Reassemble and/or select critical oritic 427. proper orifice Collection of sample Air flow rate +5% (Subsec. | Initial and Final(Subsection | Void sample. 4.3); absorbing solution at | 4.4). Check thermometer 18 +10°C during sampling | for each sample, Subsec. | Void sample. and prior to recovery 43.2 ‘Storage of sample before Store at 8° +5°C As above Void sample. analysis. _Jan. 1983 The quality control functions for analysis of samples are summarized in Table 5 2 at the end of this section 5.1. Verification of Field Record Form Procedures for verifying the field record are as follows: 1. Examine the sample record form, and invalidate the sample if vital information 1s missing and cannot be obtained from field personnel Remove the samples from the shipping container. If the shipping period exceeded 12 hours, verify that the sample temperature 1s below 10°C. If the temperature 1s above 10°C, invalidate the sample, Check t0 see that the initial and final flow rates meet the +5 percent criterion (see Subsection 4.6.2). invalidate the sample if the flow rates differ by more than 5 percent. If the flow rates differ by less than 5 percent, the average value will be used to determine the SOz concentration. Calculate the sample volume, using Equation 5-1 Vor @ ‘Ves sampling volume, std liters Q.= standard flow rate determined at the initiation of sampling, std liters/emin, Qy= standard flow rate determined ‘at the completion of sampling Std liters/min 1= total sampling time, min. 2. Log the sample into the sample- receiving log book 3. Verify the volume marked on the absorber and recorded on the sample record form against the sample volume received. If the volume received is more than 10 ml for long- term sampling (2 ml for short-term ‘sampling) lower than the volume marked on the absorber, significant leakage has occurred, Void the sample. If valid samples have <50 mi of absorbing reagent, add distilled water to bring the volume to 60 mi and continue with the analysis. ‘samples have @ volume of >50 mi, measure the volume with a graduated cylinder (Class A) and record the volume. Continue with the analysis. Valid short-term samples are ready for analysis. f samples are to be stored Equation 5-1 5.0 Analysis of Samples before analysis, place them ina refrigerator at 5°C 5.2 Colorimetric Analyses The following step-by-step procedure should be used to obtain the calibration curve for the spectrophotometer and to show the relationship of the yg of SOs to the ‘absorbance. Calibration Option 1 of, the reference method is discussed. The procedure described is intended to be used with matched spectrophotometer cells. if an unmatched pair of cells is used, the correction listed in the reference method (Subsection 2.1.11) must be applied. 1 Prepare a dilute working sult TCM solution by diluting 10 mi of the sulfite-TCM solution to 100 mil with TCM absorbing reagent. 2 Accurately pipette the indicated volumes (Table 5.1) of the sulfite-TCM solutions into six 25-ml volumetric flasks. 3. Add the indicated volumes of TCM absorbing reagent to bring the volume in each flask to 10 ml ‘4, Add 1 ml of 0.6% sulfamic acid to each, and allow to stand 10 min, 5. Accurately pipet 2 mi of 0.2% formaldehyde to each. 6. Add 8 ml of PRA solution to ‘each, and start the timer. 7. ‘Add recently boiled and cooled distilled water to bring each flask to the 25-ml mark, Mix thoroughly, 8. Place all six flasks in a water bath for at least 30 min, but no longer than 60 min, at 20°+-0.2°C. (68°+0.4°F), 9. Allow at least § min for the sspectrophotometer to warm up; adjust the zero control to bring the meter needle to infinity absorbance on the scale; standardize the light control by Section 2.1.8 inserting a 1-cm cuvette filled with distilled water into the sample holder land adjusting the light control until the meter reads zero absorbance. Note: The wavelength scale should be checked with a standard wavelength filter traceable to the National Bureau ‘of Standards initially and after each 160 hours of normal use or every 6 months, whichever occurs first. Use ‘commerically available, optically matched 1-cm cuvettes. 10. Remove the six samples from ‘the water bath, pour a portion of each fone at a time) into a cuvette, immediately read the absorbance at 548 nm, and record on the SOs Calibration Data Sheet (Figure 5.1), Compute the ug SO2/lask, using the following equation: 19 SOs = Vroms0 X Crowiso, x D Equation 5-2 where ‘View so volume of sulfite-TCM solution used, ml Crems0,= concentration of sulfur ‘dioxide in the working sulfite-TCM, ug SO2/ml from Equation 3-3) D= dilution factor (D = 1 for the working sulfite-TCM solution; 0 = 0.1 for the diluted working sulfite-TCM solution). each 25-m flask (Figure 5.2). 12. Use regression analysis to determine the slope, intercept, and correlation coefficient of the Calibration curve, (Refer to Appendix J (of Volume | of the Handbook’ for discussion of linear regression analysis.) See Figure 6.3 for calculation of the linear regression parameters. Table 5.1 Volume of Approximate Sulfite-ToM Suifite-Tom Volume of totar ‘solution solution, ml TCM, ral ug SO 00 10.0 0.0 Ditute working 50 50 36 Ditute working 100 00 72 Working 20 80 144 Working 30 70 216 Working. 40 60 288 jased on working sullite-TCM solution concentration of 7.20 ug SOz/ml. the ‘actual total ug S02 must be calculated by use of Equation 8:2 (shown in Step 10).Section 2.1.5 2 oe Instrument 1D Color Development time BS Wavelength SFE nm yg SOs/mi (Working sultte-TCM solution) LL Ong. 502 Cahbration Data Showt Temperature — Jan, 1983 SOzfme. roe, ° La “Fisorbance os B 1 . 00 0.160. ° o 3.6 [0.226 - = es 22 0.378 = ZI ! 144 0.590 3 1 ea 0.8il s | 1 28.8 1.024 Veen so Creu sop® Concentration of $02 n the working sulte-TCM solution. ng SOx/ml and D> dilution factor ‘Regression analysis results. Mossured Slope 0.05 OOS O/595 Intercept coneaioneettoon 027998 3058 33.28 1 s0v’absorbance unit $02 spectrophotameter calibration dat 4 slope Calibration factor By Figure 5.1 13. Check each new calibration curve for conformance with these eniteria a. Slope is 0.03+0 002 absorbance units/ug $02. If not, repeat the calibration. If still outside the limits, restandardize the sulfite solution and check the dye. b. The intercept 1s <0.17 absorbance units at 22°C (72°F) with 2 t-cm optical path length, and the blank 1s + 0.030 absorbance units of the regression intercept. If not, check the temperature of the water bath. If the new intercept still 1s outside the limits, check the chemicals from which the reagents were prepared and prepare new reagents ¢. The correlation coefficient 1s greater than 0.998 14. File the calculations and the calibration curve in the calibration log book. 15 Determine the calibration factor, B, (ug SO2/absorbance unt), whiett 1s the reciprocal of the slope. jolume of sullite-TCM solution used, ml Critena 0.0300.002 absorbance units/ug SO 5.3 Sample Analysis (24-h Sampling) The following step-by-step procedure 1s to be used for analysis of field samples. 1. If no leakage occurred during ‘sample shipment (as indicated by comparing the volume marked on the data form after sampling with the volume received), dilute the sample with distilled water to 50 ml If the volume is greater than 50 ml ‘measure the volume with a Class A graduated cylinder and record the volume. 2. I leakage occurred, invalidate the sample. 3. Pipette 10.0 mi of the sample into a 25-ml volumetric flask. Note: For shorter sampling periods (e g.. 1 or 3 h), quantitatively transfer the entire 10 mi sample to increase the detection limit 4 Delay the analysis for 20 min to allow any ozone to decompose. <0 170 at 22°C (add 0.015 per °C above 22°C) 5. Prepare a reagent blank by pipetting 10.0 ml of absorbing reagent into a 25-ml volumetric flask for use throughout the analytical procedure. Prepare two internal control standards containing approximately 5 and 15 ug ‘of SO2 and add absorbing reagent to bring the volume to 10 ml in 25-ml volumetric flasks, 6. Analyze the reagent blank and internal control standards before the first sample, after every subsequent 10th sample, and after the last sample. Each reagent blank absorbance should be within +0.03 absorbance units of zero, and the measured value of each internal control standard must be within + 1 ug of the true value 7. To each 25-ml flask add the following a. 1.0 ml of 0.6 percent sulfamic ‘acid (allow to react for 10 min to destroy the nitrate from oxides of nitrogen). aniys: —f—_shematche=__ eJan. 1983, Section 2.1.5 50; calibration curve EPA pararosapiine releronce method Analysis Calibration Temperature 20. DatewR2-BL Calbration actor (Bs) 3.3.2 ope nS 53-3 yj 80,/abeobance unt Sipe! = nn a8 309 — 10 oe £ os g 2 i Boe ; o2 0 ° 1016S 19580, Figure 6.2. Example of $0, cohrevon cure b. Pipette 2.0 ml of 0.2 percent formaldehyde solution. °c. Add 5 0 ml of PRA solution 8. Start the laboratory timer previously set for 30 min 9. Dilute all flasks to 26 mi with recently bailed and cooled distilled water, stopper them, and place them tna water bath at 20°4.0.2°C (68:0.3°F) 10. Set the spectrophotometer wavelength to 548 nm, and allow at least 5 min for the spectrophotometer to warm up. If necessary, adjust the zero control to bring the meter needle to infinity on the absorbance scale. ‘Standardize the light contol by inserting a cuvette filled with distilled water into the sample holder and by adjusting the light control until the meter reads zero absorbance 11. Determine as quickly and accurately as possible, the absorbance of each sample of the internal control standard and of the reagent blank Use distilled water, not the reagent blank, as the reference. 12 Record all absorbance units from the samples and the internat ‘control standard on the laboratory data form. Figures §.4a and 5 4b) 13 If the absorbance of the sample solution ranges between 1.0 and 20, the sample can be diluted 1:1 with a portion of the reagent blank and the absorbance redetermined within 5 minutes Solutions with higher absorbances can be diluted up to sixfold with the reagent blank to ‘obtain scale readings of less than 1.0, absorbance unit It is recommended, however, that a smaller portion (<10 ml) of the onginal sample be reanalyzed (if possible) if the sample requires a dilution greater than 1:1 14, Dispose of all reagents containing mercury by using one of the procedures described in Subsection 5.6. Until disposal, the discarded solutions can be stored in closed glass containers, and they should be left im a fume hood 15. Immediately after their use, clean the cuvettes with isopropanol to avoid dye deposition on the cuvette walls 16 Determine the pH of the samples in step 11. Maximum pH Sensitivity 1s 16 0.18 17, Calculate the SO concentration as follows, 9 S02/m? = 105A - Ad) BaVexD Va Va Equation 6-3 10°= conversion of liters tom? ‘A= sample absorbance ‘Ac= reagent blank absorbance By = calibration factor, ng '$02/ absorbance unit \Vn= the sample air volume corrected to 25°C (77°F) and 760 mm Hg (29.92 1n Ha), Iners, volume of absorber solution analyzed, ml Ve= total volume of solution in absorber, ml D= dilution factor (f any) required to reduce sample absorbance below 1 And calculate the SO3 concentration (pm: bm S02 = 4g SO2/m? x 3.82 x 10-4 Equation 5-4 18 If the absorbance of the blank 1s within +0.03 absorbance unis of the intercept and if the measured values of the internal control samples are within £0 07 ig/ml SO2 of the actual value, the analytical values determined for the field samples can bbe accepted as valid, If the reagent blank and/or the control sample falls outside the above limits, the reagent blank, the control sample, and the calibration curve should be checked by replication to venfy that the above limits have been met before reanalyaing the field samples. 5.4 Quality Control Check of Analysis Procedure ts recommended that each laboratory participate in the EPA rational performance audit program as an independent quality control check on the analytical method In this audit program, each participant receives five sampies each 6 mo from the US. EPA Environmental Monitoring Systems Laboratory. If the results of these five analyses all fall within the acceptable range as published in the EPA survey report, the analysis procedure 1s considered to be in control. Otherwise, the laboratory should take corrective action and analyze a second set of samples to determine if the action taken has corrected the bias or imprecision of analytical results VeSecton 2.8 ‘ Jan. 1903 Ara ronan a —~Talban marpgans airboee i : ae _——_humber. a) ty. ew ay ¥ 1 0.0 0.100 2 0.266 12.96 0.9576 0.070156. a 0378 5,84 —272/6 _0.142884 —1_ 07.36 8.4960 0.348100 _ ——5 0.6!) 466.56 75176 O65 T 72) _ i 1.024 629.44 75.64). 3.229 2 1S0BI6. ty 59/84 ry 2243637 —4 _tmumber of calibration ports} L294NZ 48576 *“Calibration Slope, Intercept, and Correlation Coefficient. The method of least squares is used to calculate a calibration equation mn the form ot where Y= corrected absorbance, m= slope, absorbance units/ug SOs 1X5 micrograms of SOs b= y intercept absorbance units) yemxeb The slope (mi. intercept (bl. and correlation coeticrent (rare calculated as follows monkey ex) Oy = 6 nb Y (6) (1568, 546)(3:224). - 0.030050 6) b -Eysmbx s (3.229) 70.930050) (75:6 = ONS9S ° € p= gf tay zety/n = {= By yn = 0.99998 Figure5.3. The performance audit program is coordinated through the 10 EPA. regional offices by the Quality Assurance Division of the Environmental Monitoring Systems Laboratory. To request further information about the program or to participate in the program, write to: ‘Ambient Air Audit Coordinator Quality Assurance Division Environmental Monitoring Systems Laboratory Research Triangle Park, North Carolina 27708 A description of the audit material for S02 analysis is given in Section 2.0.10 of this Handbook. p= (75, 229) G) Cteutation of near regression parameters 5.5 Disposal of Mercury- Containing Solutions ‘The TCM absorbing solution and any reagents containing mercury ‘compounds must be treated and disposed of by one of the two methods discussed below. Both methods remove greater than 99.99 percent of the mercury. 6.8.1 Method for Forming an Amalgam 1. Put the waste solution in ‘an uncapped vessel and place it in @ hood. 2. For each liter of waste solution, add approximately 10 g of sodium Equation 1 6)(3.229)/()I carbonate until neutralization has ‘occurred (NaOH may have to be used). 3. Following neutralization, add 10 @ of granular zinc or magnesium. 4. Stir the solution in a hood for 24 hours. Caution must be exercised, as hydrogen gas is evolved by this. treatment process. 5, After the 24 hours of stirring, let the solution stand without further stirring to allow the mercury amalgam (solid black material) to settle to the bottom of the waste receptacle 6. After the settling has occurred, decant and discard the supernatant Fiquid. "7. Quantitatively transfer the solidSection 2.1.6 Jon. 1983 (hv0y) 80) ep Arosenoge) ve'sesnBig ssyewoy fy aumeubis 4 2 uidy “7 40 opis asvenay luo seupaping yum aoueprasay ut paypuey EE HH tH fry uedesd 01 pasn suoHinos 21475 J) Wepre) 05 dorouning uN cos - s9ang 500) EEE CBT |B EOE | OPRT 2 soue | awnjon | owe qwosay | aw ay Buyduses. (u014) 607 Be a. vequinny wis [40a _qucw odes Fie Bunauwes peasouy oun 19loug "SBHAZ AIOMNZOSSection 2.1.8. 6 Jan. 1983 Preparation and Calibration Sample Analysis | a reagent water double-distiled | Colorimetric analysis Bank Frequency {and stored n'a borosiicate within 40.03 absorbance ‘of ‘lass vessel with vert guard | calibration intercept. control Reagent Container Preparation, sunimieaot, 0.6% Glass soopered Before analyts Formaldehyde. 0.2% Glass stoppered Before anslysis Sample absorbance within £1 yg SO, of actual value Absorbing reagent prepared Working iodine, "Glass stoppered, Before analysis every 6 mo, clear with 30 < pH O1n ‘dark <50 ‘Stock iodine. Gass stoppered, Yearly ‘O.01N ‘ark 24-h sampler with polypropylene | Calirauon curve for ab- Sodium thiosulfate, Glass stoppered Yearly lubes and closure with glass | sorbance vs. ug SOx/m ‘oon ‘mpinger, % and I-h sample with | slope Between 0.03 20.002 | Stock sodium Glass stoppered Yearly laih glass maget impinger ‘absorbance units/ug SOs thiosulfate, | imercept <0.17, allponts | OIN ‘against specihicauon. S04) of best-fit curve Working sullite-TCM solution accurately prepared from standard Solution prior to analysis, stable or 30 days at 8°C (41°F) if stored in All data points within +2% of the dark glass-stoppered bottle best-ta calibration curve for How. | ‘measuring rotameter ‘Standard sulfite-ICM solution 320-400 pg SO/ml Flow rate measured before and | Pararosanuline (PRA) reagent 100% assay: stable if stored in dark ‘sher each sampling period ‘g/ass-stoppered bottle Rotameter cleaned and calibrated every 30 days of operation or every 6 mo Assayed PRA stock solution stored in dark glass-stoppered bottle: Solution prepared it slope of calibration curve deviates from 0.03 0.002 Sample umer within 18 min/ Analytical balance performance within 20.1 mg of manufacterer's speciheauons | | | | | Check of flow-measuring device | within 0.04 wg SO2/ml (1 ug | Figure5.4B8 Laboratory data log fbackside) material to @ container and allow it to ary. 8, The solid material can be sent to a mercury reclaiming plant. It must not be discarded 5.5.2. Method Using Aluminum Foil Sirpps 1. Put the waste solution in an luncapped vessel and place it im a hood, 2. For each liter of waste solution, add approximately 10 g of aluminum {oil strips. fall the aluminum appears 10 be consumed and no gas is evolved, add an additional 10 g of foil Repeat until the foil is no longer consumed and allow the gas to evolve for 24 hours. 3. Decant the supernatant liquid and discard, 4, Transfer to a storage container the elemental mercury that has settled to the bottom of the vessel 5. The mercury can be sent to a mercury reclaiming plant. It must not be discarded.Jan, 1983 7 Table5.2 Activity Matrix for Analysis of Samples @ Activity Section 2.1.6 Action if Frequency and method requirements Acceptance limits of measurement are not met Verification of field record form Flow rate check of system Calibration of spectrophotometer Reagent blank and internal control standard All vital information obtained and verified Ditterence in initial and final flow rates after ‘sampling <5% Each calibration curve: Slope 0.03 +0.002 ab- ‘sorbance unit/ug SOx intercept <0.17 absorbance units: each correlation coefficient >0.998 Analysis in accordance with Subsec. § 3; absorb- ance of blank within £0.03 absorbance units of zero: ‘measured value of each internal control standerd within 1 ug SO2 actual value Visually inspect after each sampling period. Repeat flow rate measure ‘ment after sampling. Check the calibration curve atter sampling Analyze a reagent blank ‘and internal control ‘standard before the first samples, atter every sub: Sequent 10th samples and after the last sample Obtain missing data or invalidate the sample. Invalidate the sample. Repeat calibration and/or standardize the sulfite solution, and check dye: ‘check water bath temp. and/or check chemicals used to prepare reagents: repeat reading for that point; average new and original values; replat Take corrective action (recalibrate it necessary) and reanalyze the last 10 samples.Jan. 1983 1 Section 2.1.6 6.0 Data Reduction, Validation, and Reporting ‘The quality control activities are summarized in Table 6.1 at the end of this section 6.1 Flow Rate Data Review Samples should be invalidated if the difference between the initial and final flow rate is greater than 5 percent 6.2 S02 Data Review The analytical data should be invalidated if any of the following Conditions exist regarding SO, calibration. 1. Fresh reagents are not used. 2. The internal control samples were analyzed, and the results deviated by more than +1 1g SOz from the known value, but a new calibration curve was not constructed. The slope of the final calibration curve was nat within 0.03 £0,002 absorbance units/ug SO2. 4. The intercept of the final calibration curve was not <0.17 at 22°C (72°F) with a 1-cm optical path length, and/or the blank was not within +0.03 of the regression intercept. 5. The correlation coefficient of the least square regression was <0.998 6.3 Standardize Format Reporting The standardized procedure for reporting is as follows 1. Record the 24-h sample analytical results on the SAROAD daily data form (Figure 6.1), 2. Record the 30-min or the 1-h ‘sample analytical results on the ‘SAROAD hourly data form (Figure 62) 3. Refer to EPA-450/2-76-029, Dec. 1976, OAQPS Guidelines, AEROS Manual Serves, Volume I ‘AEROS User's Manual, U.S, EPA Office of Air and Waste Management, Research Triangle Park, North Carolina.Section 2.1.6 2 Jan. 1983 24-Hour or Greater Sampling Interval 21 Smelter own Pollution Control r ) 1 gener Site Area Ste —pmelter Town __________ (arg oralolo lols £00 Worth Street ger Frye © re aon Bae Aadress 802 Network _2# ovr (P] {olz| [7] [7[4} [o[z) Fare Tine interval 7 oR 116 17 Te SO — _ ome Tame Tame | ware pananieren panamerer pananrer panainerer Code Code cove ove ° | 4izwiol7] |_LLLLL) LTT) 232475 26-27 3 38 3940 7 Penne |e wee 7A (17) fo] (LLILOO } 2 wa 2 |\fe www @ wn RT 19 20.21 22. "3934 38 96. 4748.49.60 “8 16 77-78 oT 1o}o) felatz{s E | 2lolol felalzié | | | fofet T | | “TI | +t | Pots{ | I { | { BAS ood | EES ofsl | [ | + +— | oe | | 4 | 1 TotW] i CI Cen tft] fi | —— r+ | bo2zt4 - J | i Crest] lea al 14 } | t | i \ { 1 i i{s i peal I 4 | tte | | | oe rz 1 iL Cre 1 | CPT rps | el] rete | A C ait t | —| Be I ts i | I io ee 2.5 y Ly yyy | 216 a lett Tf 7 [EC zfe|_| | am | Z| 7 C 7 { i o- 204892 1 O aoe sret 43270 o3210 Figure6 1 SAROAD doy data ormSection 2.1.6 Jan, 1983, Ze |Aola\e loll olo|o[olalololo|ale/olo\o fe [ele[o ol jojolojojolols|o ojala] oe ° zitoy | on 4 mp Ninoy avOWWS Fg einbLy E|O Oo) 4|0|AAO) a|A|A| O[0/0] 3] 10/0) @ 7[o[919[ 7[O[a|0] 7fo|o|o} 7/9] efofolajojojalojojojolo ° ZZ pu | 01 Spy 6 py 8 Spy 9 Spy g Spy Spy |g bpy 2 Spy 1 Opy aH as! keg ze 1 of 6k 8 28 SE be Ee e a0, sw __s90 1p ours ons Zz] 412] BI) Vielzlz|4 Wed Apaoy Yao aH TOD RoR Gar lemme rower __pauseye sntureg ssompy 015 archon shes —_ 2 _ ia FUG OF Fees GH Oe V/\ [slZ] (4 [Z] : : fe owen h9 aceite meng oor) cet ” ee O16 o£ 9 yueg e10g 2naWi0.y /euoney Asueby 7je|efolo AINIDY NOUD310Ud TYINIMNOIANT BAG Tey] au ais ensewuy Bunctues non-ye veuL S507Section 2.1.6 4 Jan. 1983 6.4 Filing the Calculat 1. Identify all of the sample calculations with the sample numbers and dates. 2. File the calculations in the laboratory data log book. Table6.1 Activity Matrix for Data Reduction, Validation, and Reporting Action if Frequency and method requirements Activity _ Acceptance limits ____ of measurement _ are not met Flow dota Deviation in flow rates Visually observe reported Void the sample less than 5% data S02 data Five conditions of Sub As above As above sec 6.2 met Documentation and report All needed data available As above As above of results.Jan, 1983 7.1. The 24-h Bubbler Train Every 3 months or every 15 sampling periods, whichever occurs first, the following components should be replaced 1. Membrane filter - Replace the membrane filter by removing the Tygon tubing from the inlet and outlet of the plastic fiter holder (The fiter and filter holder are disposable ) Seal the new filter holder to prevent leakage by pulling the filter holder apart and coating the junction of the two halves with a thin layer of cyclohexanone and by rejoining the two halves and pressing them together until they are dry Connect the new filter in place 2 Mist trap ~ Change the trap by removing the Tygon tubing and replacing it with a clean dry trap Disassemble the trap that was, removed, wash it, and allow it to dry before reassembling and using it again 3. Rubber septa - Remove the old septa from the glass adapters, and replace them with new septa 4. Vacuum gauge - Check the vacuum gauge against a calibrated vacuum guage or a mercury manometer. Replace the guage if its defective, (not within +25 mm (1 in) Hg). 5 Vacuum tubing - Replace the black vacuum tubing with @ new section to minimize the possibility of leakage. 7.0 Maintenance 6 Vacuum pump - If the vacuum pump cannot provide >530 mm (>21 in) Hg vacuum at 760 mm (29.92 in) atmospheric pressure, replace ts carbon vanes or its diaphragm. At an atmospheric pressure of 760 mm, the 530 mm (21 inj Hg vacuum provides a safety margin of 100 mm (3.9 in) Hg vacuum 7.2. The Short-Term Sampling Train Every 3 months or every 30, sampling periods, whichever occurs Section 2.1.7, 7.3 Calibration Equipment and Related Apparatus Periodic maintenance requirements {for equipment such as the mass -flow meters, soap-bubble meters, and spectrophotometers vary with the specific manufacturer. Thus, the manufacturer's recommendations should be followed as well as one’s own experience. first, the following components should be serviced 1 Rotameters - Disassemble and clean the rotameters with detergent, and rinse with distilled water and alcohol Recalibrate before use 2 Mist trap - Clean the trap, and replace the glass wool 3 Needle valve - Inspect the valve {for proper seating of the stem, check the vaive-siem packing nut for proper tension, and clean the valve with detergent Rinse with distilled water and alcoho! 4. Vacuum pump - Perform the same maintenance as that described tn Subsection 7 1 5. Vacuum tubing - Perform the same maintenance as that described in Subsection 71 Table 7.1 Activity Matrix for Regular and Preventive Maintenance Action if Frequency and method requirements Equipment Acceptance limits ‘of measurement re not met _ 24-h bubbler train ‘Membrane filter. mist rap. Replace every 3 moor after Implement maintenance rubber septa, and vacuum — 18 sampling periods. actions. tubing replaced regularly Vacuum gauge Vacuum pump Readings correct within 426-4 mm (41 in.) Hg Capability to provide at Check every 3 mo against calibrated vacuum gauge Replace it defective. or Hg manometer. Teast 530 mm (21 in) Hg vacuum at STP. Short-term sampling train Rotameter, mist trap needle valve, vacuum ‘pump, and vacuum ser- viced regularly. Calibration equipment and related apparatus Maintained periodically according t0 manufac: turer's recommendations. Test the vacuum. Clean every 3 mo or after 30 sampling periods. Follow manufacturer's recommendations. Replace carbon vanes or diaphragm: retest. Implement maintenance ‘actions. Implement maintenance ‘actions,Jan. 1983, 1 Section 21.8 ‘An audit is an independent assessment of the accuracy of data, Independence is achieved by having the audit made by an operator other than the one conducting the routine ‘measurements and by using audit ‘standards and equipment different trom those routinely used in ‘monitoring, The audit should be a true assessment of the measurement process under normal operations— that is, without any special preparation or adjustment of the system. Routine quality assurance checks conducted by the operator are necessary for obtaining and reporting {good quality data, but they are not Considered part of the auditing procedure. Two types of audits are recommended herein—performance audits and system audits. Three performance audits and one system audit are detailed in Subsections 8.1 and 8.2 and summarized in Table 8.2 (at the end of this section}. In addition to these audits, the precision of the entire measurement process is assessed by comparing the ‘measurements made by collocated samplers, as described in Sections 2.0.9 and 2.1.8. Proper implementation of an auditing program serves a twofold purpose: to ensure the integrity of the data and to assess the accuracy of the data. The technique for estimating the accuracy of the data is given in Section 2.08 of this volume. 8.1 Performance Audits Performance audits conducted by another operator/analyst are quantitative evaluations of the quality of data produced by the total ‘measurement system (sample collection, sample analysis, and data processing). The following three performance audits of individual variables are recommended: 1. Audit of flow rate for sample collection. 2. Audit of analysis process by use of reference samples (mandatory). 3. Audit of data processing. (Refer to Appendix A for auditing frequency.) Auditing of 7 of 100 sampling periods for each site is suggested as a Starting frequency for the first and third audits; frequency for the second audit is given in Subsection 8.1.2 8.0 Auditing Procedure Where one sample is collected every 6th day, one audit per month at each site is recommended: if the data are reported quarterly, this would mean auditing 3 of each 18 sampling periods. if the number of sampling periods 1s >16 but <0, four audits are recommended. These are the suggested starting frequencies: they should be altered if either experience fr data quality indicate a need for change. For example, the frequency should be reduced if experience indicates that data are of good quality; the opposite would apply if the data were of poor quality In a determination of the number of audits needed, itis more important to be sure that the audit sample is representative of the various conditions that may influence the data {quality than to adhere to a fixed frequency. The supervisor will specify the frequencies according to ‘mointoring requirements, 8.1.1 Flow Rate Audit - For 30-mit 1-h, and 24-h samples, a flow rate audit is recommended to assess the sampling collection phase of the ‘measurement process. The audit should be performed as follows. 1. Have the regular operator the sampler for sample ‘usual; this must include filling in the sample record form Figure 4.10) 2. Have the operator compute the average sampled volume, Viv aS measured by the regular flow measurement device and corrected to reference conditions (if necessary) 3. Insert the audit device in the ‘sample inlet line and measure the flow in the usual manner at the beginning and at the end of the sampling period. 4. Calculate the average audited volume, Vat reference conditions for liters/minute and t is the sampling time in minutes). 5. Compute the percent difference, (a measure of inaccuracy): d=(Vn=Va) 100. ve Equation 8-1 6. Record Vin. Vs, and d. tis recommended that the d's be plotted fon the X-and-R chart as illustrated in Figure 8.1. (Only the X chart is used for quality control of accuracy, the standard X-and-R chart 1s used for convenience.) If d is greater than 7% oF if Vn/ Va does not fall between 0.93 and 1.07, begin the troubleshooting and take corrective action before resuming the sampling, All flow rate data for the audit period is invalidated if an unexplained malfunction has occurred and resulted in errors in the flow rates, 8.1.2 Audit of Analysis Process Using Reference Samples - Reference (audit) samples should be included at ramdom at the recommended frequency among the samples awaiting analysis. If possible, they should not be recognizable to the analyst as reference samples. The ‘audit procedure for the SOz method is 2s follows 1. Prepare the audit solutions from ‘2 working sulfite-TCM solution, as described previously in Subsection 3.12 of Section 2.1.3. Prepare these ‘audit samples independently from the standardized sulfite-TCM solution Used in the routine analysis procedure. Prepare new sulfite-TCM ‘audit samples every 30 days, and ‘store them between 0° and °C. 2. Prepare the audit samples in ‘each of the concentration ranges of 0.2 100.3, 0.5 100.6, and 0.8 0.0.9 19 SO2/mi.* Analyze an audit sample in each of the three ranges at least ‘once each day that samples are analyzed and at least twice per calendar quarter. The differences between the measured concentrations (Vg $O2/mi) and the audit concentrations are used to calculate the percent difference (a measure of inaccuracy! as described in Section 2.0.8. The calculation for percent difference for individual audit samples is also shown here at Item 3. 3. The agency/organization determines the percent difference (d) between the measured SOs concentration and the audit or known Sis same acjurrmant eNovié be applied al Corterponding ara in ths sectonJan. 1983 Section 2.1.8 (ae ‘uonay 3201109) sou: ro {| | | uy sebu0y Wie Ie ar za ua . _ bexlzcpa-bsspozlaox|zor/levoez|nelevr|s zee léect 7 ue = a | | X Wesay an! 4 — — — —- i cat _ - _ |_| ie | : ‘J soe] czpeE roe oe weleerrerleerigerver\Zér| 7e|7#|2|2 | F LC —_ 7 a sep cr ip sels lade rarer Por| of ros! x bus|ser|z0c| | * @ C ase J [| [ { ee | | CI ale t+ Po ez jaeperha [i _ { Bees [Ee re 17e ke th Peele Peep Gonusosnseay, ea y pe x | % 7 27 Sn SBW ATO BL PIPE POITELIW i BDU STEHT peu —————opny area sutra y mi suns CUPL V ET ar gt eta oor ee men ‘peteJan. 1983 values of concentration. The dis @ measure of both the bias and the random error of the analytical phase of the S02 reference method. Calculate d by using Equation 8-2, See Cree A a) Csoe Equation 8-2 where Cao, (M)= concentration measured by the lab analyst ug/ml C20, (A)= audit or known concentration of the audit sample, ug/ml The recommended contro! limits for the three audit sample ranges (0.2 10 0.3, 0.5 10.06, and 0.8 100.9 ug '$02/mi) are the 90th percentile value for d based on the results of five audits (11/76, 4/77, 10/77, 4/78, and 10/78) performed by the Environmental Monitoring Systems Laboratory, USEPA, Research Triangle Park, North Carolina.” "° By definition, 90 percent of the laboratory participants in the audit obtained values of d less than the values tabulated below. The control limits axpected to be exceeded by 10 percent of the laboratories to be audited, based on these five audits. The 90th percentile values and the known audit concentrations are given below for each audit concentration, range. 3 Section 2.1.8 Based on the results or these five audits, the recommended 90th Percentile control limits for audit ‘samples are +33 percent for the 0.2 t0 0.3 ug SO2/ml concentration range and +18 percent for both the 0.5 to 06 and the 0.8 10 0.9 ug SOz/m! concentration ranges. itis recommended that each laboratory participate in the EPA National Performance Audit program as described in Section 2.1.5, Subsection 5.4. This will serve as an independent audit of the analysis technique. 8.1.3 Data Processing Audit - The data processing audit is most conveniently performed soon after the original calculations have been completed, so that corrections can be made immediately and additional explanatory data can be retrieved from ield personnel when necessary. The procedural stops are as follows. 1. The audit must be performed by an individual other than the one who originally reduced the data. The check should start with the raw date and conti ‘ough the recording of the concentration (ug SOz/m) on the ‘SAROAD form. 2. if the mass concentration of SOz computed by an audit does not agree with the original or indicated value within round-off error, the calculations for all samples collected since the previous audit should be checked and corrected. The audit value is always reported as the 0.2 10.0.3 yg SOz/mi _ ‘Known audit concentration 90th percentile ford. Audit date ug SO_/ml % 11/76 0.259 33 477 0.289 32 10/77 0.338 35 0.5 100.6 yg SO/mi ‘Known audit concentration 90th percentile ford. Audit date SOo/ml % 11/76 0.617 24 “7 0.688 17 10/77 0.562 18 10/77 0.562 duplicates 17 10/78 0.533 18 0.8 100.9 yg SO/mt ‘Known audit concentration 90thpercentile ord. Audit date. 'S0;/ml % 11/76 0.895 18 4/77 0.930 23 10/77 1.07 16 4/78 0.755 7 10/78 0.757 7 correct value, under the assumption that the audit should be checked if a discrepancy exists and corrected if necessary. 3. The audit and the original values and the percentage difference should bbe recorded in the laboratory log book and reported to the supervisor. 8.2 System Audit A system audit is an onsite inspection and review of the quality assurance system used for the total ‘measurement system (sample collection, sample analysis, data processing, etc.) A system audit is a ‘qualitative appraisal of system quality. ‘A system audit should be conducted at the startup of a new monitoring system and thereafter as appropriate to ascertain significant changes in system operations. A checklist for use in a system audit is provided in Figure 8.2. These questions should be reviewed for their applicability to the particular local, State, or Federal agency being auditedSection 2.1.8 4 Jan, 1983 1. What type of manual sampler 1s used for SOs collection? (a) BAC @DSport (c)2-port (4 other — = 2 Ie sraight tube mpingr used nthe pohpronyione sampling tube? eg b= 3 15 sample probe made of accepted materia? Teflon, Glass Pe 4 le the roe ond mano) cated pig mag urggardeneyon whe vambling n hun ongtone age 5 Woot imaiod of salen sis lnc eget Ina copy avatatesggaane (Mei should be om 40 CER 50, July 1, 1982. as amended 47 FR 54896, Decerhber 6, 1982 and 48 FR 17955, Apri, 1963 6 i Wihet quality of reagents is sed 'o makeup the ehenveos forthe Sr aelyan? Legale {they Shut be reagent grade ber 2. Is the sampling train routinely checked for leaks? — : tow otra) Once a weet, (6) Gnce roth, (Mone a cvarter (aot sana, 8. What calration check procedure is used for flow measuring device used i the Held? 72.1.2 ID Isa writen copy avarlable? 9. Are sampling low rates detefmnined before and after each sampling period? Is thera an established procedys for isang needs that are not wth flow ae nts ical? aglaw at eats? LAB 2 (any needle outs of 180 t0 200 e”m/min should be discarded for 24% samples) Is the absorbing solution mamntained af 15° 1 Bee Are samples vere? gta Do nal and tinal How rte agree within = agama iors sample they 70 me) 10, Have calibration curves been made, ad are they avalable? 75 ug SO2/m?, the 3¢ limits of agreement are about 45 percent of the average concentration: for low concentrations these limits often exceed 100 percent. Based on experimental data in Table 9.1 and on the actual field test data, poor agreement may be expected between collocated samplers when measured concentrations are <75 ug S02/m?. 9.2 Accuracy The accuracy of the pararosanil method for measurement of SO is assessed as described in Section 2.1.8, Auditing Procedure. The accuracy of a single instrument is calculated as shown in Section 2.0.8 and 2.1.8 of this volume of the Handbook Experimental Data and Expected Agreement Between Two Collocated SOz Sampling Trains on a Common Expected agreement between collocated (two) sampling trains® ‘Ba-control limits Relative - Standard standard Percentage of Average (X) deviation (s) deviation average 11g SOz/m? SO3/m? (100s/%) SOa/m? concentration. 16.7 2.53 15.1 10.7 64 35.6 452 127 192 54 378 313 83 13.3 35 712 454 64 193 27 724 117 16 50 7 73.8 3.43 46 14.6 20 77 581 33 246 14 201 3.37 1.7 143 7 344 261 08 ny 3 684 78 26 785 n 694 271 39 15 7 927 449 48 190 20. “Based on 24-h samples obtained by one analyst using five trains on @ common manifold (Fuerst, R.G. Effect of Temperature on Stability of Sultur Dioxide Samples. Unpublished research by the Environmental Monitoring and Support Laboratory, Research Triangle Park, N.C, March 1976) "Results in columns 4 and 5 (calculated by multiplying the results in columns 2 and 3, respectively by 32) were plotted as an eye-fitted smooth curve (Figure 9-1) to provide 3a control limits which represent the best agreement that might 2 expected for collacated samplers using the S02 Reference Method.Section 2.1.9 2 Jan, 1983 for the percent difference (i) 0, control (99 7%) hit beween collocated samplers ° 700 "200-300 "400 500600, 700800 "900-7000 ‘Mean Concentration, ug SOx/m? Figure 9.1 Agreement between collocated (two) SO; sampling treins under well-controlled conditions (besed on laboratory ‘experimental data in Table 9.1)Jon, 1983 Two considerations are essential to achieving data of the desired quality (1) the measurement process must be ina state of statistical control at the time of the measurement, and (2) when the systematic errors are Combined with the random variation {errors of measurement) the result must be @ suitably small uncertainty Evidence in support of good quality data is acquired by performing quality control checks and independent audits of the measurement process, documenting these data, and using materials, instruments, and measurement procedures that can be traced to an appropriate standard of reference Data must be routinely obtained by repeat measurements of standard reference samples and primary, secondary, and/or working standards, and 2 condition of process control must be established. The working calibration standards should be traceable to standards of higher oO: such as those presented here 1. Class-$ weights (NBS specifications) are recommended for the analytical balance calibration. (‘See Section 2 1 2 for details on balance calibration checks ) 2. Sulfur dioxide permeation tubes should be traceable to NBS Standard Reference Materials, Numbers 1625: 1627" (See Section 2111 Subsection 10.3, for details on calibration using SOs permeation tubes.) 3. Reagents should be at least ‘American Chemical Society (ACS) reagent-grade chemicals. Such agents have been certified to contain impurities in concentrations below the specifications of the Committee of Analytical Reagents of the ACS. Each reagent bottle 's identified by ACS with a batch umber Potassium lodate reagent ‘must be of primary standard quality. 4 The complete absorbance scale should be checked with a calibrated set of NBS filters (GRM’s 2101 2105") periodically and anytime a control sample cannot be measured within the control Iimit assigned to it (See Section 2.1.5 for details of spectrophotometer calibration | 5. The spectrophotometer should be checked for proper wavelength calibration throughout the range of 1 Section 2.1.10 10.0 Recommended Standards for Establishing Traceability the instrument. A Didymium Glass filter* may be used. This filter has five well-defined absorbance maxima between 400 and 900 mm. The known peak maximum at 685 mm should agree within + 6 mm of the ‘measured peak maximum or remedial action should be taken. 6. All calibrations of flow measurement devices are directly traceable to primary displacement methods. “Avalable trom Arthur H Thomas Company (Paiadelania, Pennsyivana)Jan, 1983, Appendix A—Reference Method for the Determination of Sulfur Dioxide in the Atmosphere (Paraosaniline Method) [Appendix A revised by 47 FR 54899, December 6, 1982) 1.0 Applicability 1.1 This method provides a measurement of the concentration of ‘sulfur dioxide (SOs) in ambient air for determining compliance with the primary and secondary national ambient air quality standards for sulfur oxides (sulfur dioxide) as ‘specitied in § 60.4 and § 50.5 of this chapter. The method is applicable to the measurement of ambient SO: ‘concentrations using sampling periods ranging from 30 minutes to 24 hours. Additional quality assurance procedures and guidance are provided in Part 58, Appendixes A and B, of this chapter and in references 1 and 2 2.0 Principle. 2.1 A measured volume of air is bubbled through a solution of 0.04 M potassium tetrachloromercurate (TCM). The SOz present in the air ‘stream reacts with the TCM solution to form a stab! ‘monochlorosulfonatomercurate(3) complex. Once formed, this complex resists air oxidation (4, 6) and is, stable in the presence of strong oxidants such as ozone and oxides of nitrogen. During subsequent analysis, the complex is reacted with acid- bleached pararosaniline dye and 10 form an intensely rosaniline methyl sulfonic acid(6}. The optical density of this species is determined ‘spactrophotometrically at 848 nm and is directly related to the amount of SOs collected. The total volume of a sampled, corrected to EPA reference ‘conditions (26°C, 760 mm Hg [101 kPa), is determined from the measured flow rate and the sampling time. The concentration of SOs in the ambient air is computed and expressed in micrograms per standard cubic meter (ug/std m?) FaO.GER 60, Jty 1, 1982, 08 emenaed 47 FA 12817985, 1 Section 2.1.11 11.0 Reference Method 3.0 Range. 3.1. The lower limit of detection of S02 in 10 mL of TCM is 0.75 ug (based on collaborative test results) (7), This represents 9 concentration of 25 49 SO2/m: (0.01 ppm) in an air ‘sample of 30 standard liters (short term sampling) and a concentration of 13 4g SO2/m* (0.005 ppm) in an air sample of 288 standard liters (long- term sampling). Concentrations less than 25 ug SOz/m? can be measured by sampling larger volumes of ambient air; however, the collection efficiency falls off rapidly at low concentrations (8.9). Beer's law 1s adhered to up to 34 119 of S02 in 25 mL of final solution. This upper limit of the analysis range represents a ‘concentration of 1.130 jg SO2/m? (0.43 ppm) in an air sample of 30 ‘standard liters and a concentration of 590 19 SO2/m? (0.23 ppm) in an air sample of 288 standard liters. Higher concentrations can be measured by collecting a smaller volume of air, by Increasing the volume of absorbing solution, or by diluting a suitable portion of the collected sample with absorbing solution prior to analysis. [Corrected by 48 FR 17365, April 22, 1983) 4.0. Interferences. 4.1, The offects of the principal potential interferences have been minimized or eliminated in the following manner: Nitrogen oxides by the addition of sulfamie acid (10, 11) heavy metals by the addition of ethylenediamine tetracetic acid disodium salt (EDTA) and phosphoric ‘acid. (10, 12) and ozone by time delay (10) Up to 60 yg Fe (i), 22 ua V (VI, 10 pg Cu (I), 10 jag Mor Ui), and 104g Cr ill) in 10 mL absorbing reagent can be tolerated in the procedure (10). No significant interference has been encountered with 2.3 14g NHs (13), 5.0 Precision and Accuracy. 6.1. The precision of the analysis is 4.6 percent (at the 95 percent confidence level) based on the analysis of standard sulfite samples (10, 5.2 Collaborative test results (14) based on the analysis of synthetic test atmospheres (SOs in scrubbed air) using the 24-hour sampling procedure and the sulfite-TCM calibration procedure show that © The replication error varies linearly with concentration from +£2.5 g/m? at concentrations of 100 119/m? to £7 g/m? at concentrations of 400 g/m. © The day-to-day variability within an individual laboratory (repeatability) varies linearly with concentration from +18.1 g/m? at levels of 100 ug/m? to +60.9 g/m? at levels of 400 yxg/m* © The day-to-day varvability between two or more laboratories (reproducibility) varies linearly with concentration from +36.9 g/m? at levels of 100 g/m? to 103.5 g/m? at levels of 400 g/m. '@ The method has a concentration dependent bias which becomes significant at the 95 percent confidence level at the high concentration level. Observed values tend to be lower than the expected SO. concentration level. 6.0 Stability. 6.1 By sampling in a controlled temperature environment of 15° +10°C, greater than 98.9 percent of the SOz—TCM complex is retained at the completion of sampling (15). If kept at 5°C following the completion ‘of sampling, the collected sample has been found to be stable for up to 30, days (10). The presence of ETA enhances the stability of SOs in the TCM solution and the rate of decay is independent of the concentration of S02 (16). 7.0 Apparatus. 7.1 Sampling 7.1.1 Sample probe: A sample probe meeting the requirements of Section 7 of 40 CFR Part 58, Appendix E (Teflon® or glass with residence time less than 20 sec.) is used to transport ambient air to the ‘sampling train location. The end of the probe should be designed or oriented to preclude the sampling of precipitation, large particles, etc. A Suitable probe can be constructed from Teflon® tubing connected to an inverted funnelSection 2.1.11 2 7.1.2 Absorber—short-term ‘Sampling: An all glass midget impinger having a solution capacity of 30 mL and a stem clearance of 4:1 ‘mm from the bottom of the vessel is used for samplying periods of 30 minutes and 1 hour (or any period Considerably less than 24 hours) ‘Such an impinger is shown in Figure 1. These impingers are commercially available from distributors such as ‘Ace Glass, Incorporated, 7.1.3 Absorber—24-hour sampling: A polypropylene tube 32 mm in diameter and 164 mm long (available from Bel Art Products, Pequammock, NJ) is used as the absorber. The cap fof the absorber must be a polypropylene ‘cap with two ports (rubber stoppers. are unacceptable because the absorbing reagent can react with the ‘stopper to yield erroneously high SOz concentrations). A glass impinger ‘stem, 6 mm in diameter and 158 mm long, is inserted into one port of the absorber cap. The tip of the stem is tapered to a small diameter orifice (0440.1 mm) such that a No. 79 jeweler’s drill bit will pass through the ‘opening but a No, 78 drill bit will not Clearance from the bottom of the absorber to the tip of the stem must be 62 mm. Glass stems can be fabricated by any reputable glass, To Sample —¢@— abe tnoingors (800 Bee 20 mt Emm io be 20m vom £ 10 mm 0.0. 24/40 Concentric with J outer piece and with hose Groduations at § mi intervals. All the ‘way around. ‘Nozale 1D. Exactly Pieces should be inter changeable, maintaining OD. Inside ‘nozzle centering and Clearance clearance t0 bottom 3105 mm Inside surface Figure 1. Short term sampling train, 1 mm: passes 0.09 t0 0.11 cfm at 12 in. HO vacuum. blower or can be obtained from @ scientific supply firm. Upon receipt, the orifice test should be performed to verify the ontfice size. The 50 mL volume level should be permanently ‘marked on the absorber. The assembled absorber 1s shown in Figure 2 7.1.4 Moisture trap: A moisture trap constructed of a glass trap as shown In Figure 1 or a polypropylene tube as shown in Figure 2 15 placed between the absorber tube and flow control device to prevent entrained liquid from reaching the flow control device The tube 1s packed with indicating silica gel as shown in Figure 2. Glass wool may be substituted for silica gel when collecting short-term samples (1 hour or less) as shown in Figure 1, o for long term (24 hour) samples if flow changes are not routinely encountered 7.1.5 Cap seals: The absorber and moisture trap caps must seal securely to prevent leaks during use. Heat shrink material as shown in Figure 2 can be used to retain the cap seals if there is any chance of the caps. coming loose during sampling shipment, or storage 7.1.6 Flow control device: A calibrated rotameter and needle valve Hypodernue > Te vacuum Pump Critical Ortice Flow Control (tlt tovcsm | Needle a Alternative Flow Control Glass Wool or ‘Sitea Ge! All-Glass Midget Impinger (Ths 18 @ commercially stocked item) Jan. 1983 combination capable of maintaining and measuring air flow to within +2 percent is suitable for short-term ‘sampling but may not be used for long-term sampling. A critical onifice ‘can be used for regulating flow rate {or both long-term and short-term sampling. A 22-gauge hypodermic needle 25 mm long may be used as a cntical oniice to yield a flow rate of approximately 1 L/min for a 30- minute sampling period. When sampling for 1 hour, a 23-gauge hypodermic needle 16 mm in length will provide a flow rate of approximately 0.5 L/min, Flow control {for a 24-hour sample may be provide by a 27-gauge hypodermic needle ertical orifice that is 9.5 mm in length. The flow rate should be in the range of 0.18 to 0.22 L/min 7.1.7. Flow measurement device: Device calibrated as specified in 9.4.1 and used to measure sample flow rate at the monitoring site. 7.1.8 Membrane particle filter: A membrane filter of 0.8 to 2 um porosity is used to protect the flow Controller from particles during long- term sampling. This item is optional for short-term sampling 7.1.9 Vacuum pump: A vacuum Pump equipped with a vacuum gauge and capable of maintaining at least 70 kPa (0.7 atm) vacuum differential ‘across the flow control device at the specified flow rate is required for sampling, 2.1.10 Temperature control d The temperature of the absorbing solution during sampling must be maintained at 15° + 10°C. As soon as possible following sampling and until analysis, the temperature of the collected sample must be maintained ‘at 6° + 5°C, Where an extended period of tume may elapse before the collected sample can be moved to the lower storage temperature, a collection temperature near the lower limit of the 18 = 10°C range should be used to minimize losses during this period. Thermoelectric coolers. specifically designed for this temperature control are available commercially and normally operate in the range of 5° to 18°C. Small refrigerators can be modified to provide the required temperature control; however, inlet lines must be insulated from the lower temperature to prevent condensation when sampling under humid conditions. A small heating pad may be necessary when sampling at low temperaturesTetlon, Polypropylene, or Glase Guess Imonger ‘stem ‘Absorber for 24h Sampler Note. A midget impinger is used for 1 hour sampling (<7°C) to prevent the absorbing solution from freezing (17). Figure 2. 24-Hour sampling system 7.1.11 Sampling train container: The absorbing solution must be shielded from light during and after sampling. Most commercially available sampler trains are enclosed in a light- proof box 7.1.12 Timer: A umer 16 fecommended to initiate and to stop sampling for the 24-hour period, The lumer is not a required piece of ‘equipment; however, without the timer a technician would be required to start and stop the sampling manually. An elapsed time meter is also recommended to determine the duration of the sampling period. 7.2. Shipping. 7.2.1. Shipping container: A shipping container that can maintain @ temperature of 5° + 5°C 1s used for transporting the sample from the collection site to the analytical oratory. Ice coolers or refrigerated shipping containers have been found to be satisfactory. The use of eutectic Cold packs instead of ice will give a Polypropylene 2 Port Tube Closure 3 Section 2.1.11 more stable temperature control. Such equipment is available from Cole- Parmer Company, 7425 North Oak Park Avenue, Chicago, IL 60648, 7.3 Analysis 7.3.1 Spectrophotometer: A spectrophotometer suitable for measurement of absorbances at 548 nm with an effective spectral bandwidth of less than 15 nm is required for analysis. If the ‘spectrophotometer reads out in tranamitance, conver to absorbance as follows, A= logo (1/7) ” where A= Absorbance, and ransmittance (0

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